Use of extended surfactants in process membrane cleaning

ABSTRACT

Disclosed are membrane separation cleaning processes and clean in place compositions for such membranes. The cleaning compositions can remove proteins, fats, and other food, beverage, and brewery based soils and offer an environmentally friendly alternative surfactant system to NPE. Branched extended chain PO/EO nonionic surfactants with certain characteristics may be used to provide superior cleaning to membranes. The specific surfactants may be used alone or in combination. In some embodiments, the surfactant package is used as part of a cleaning composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to provisional application U.S. Ser.No. 62/565,361 filed Sep. 29, 2017, which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

Described herein are methods and compositions for cleaning membranesused in separation facilities. The cleaning compositions can removeproteins and fats and offer an environmentally friendly alternativesurfactant system to nonyl phenol ethoxylate (NPE). The applicationincludes a surfactant additive or booster system that can form part of acleaning composition or can be used alone for improving the cleaningproperties of cleaning solutions as well as improve the performance ofthe membrane by cleaning the surface and minimizing subsequent proteinor soil fouling during the following processing run.

BACKGROUND OF THE INVENTION

Membranes provided within a separation facility can be treated usingclean-in-place (CIP) methods to provide flushing, rinsing, pretreatment,cleaning, sanitizing and preserving, as filtration membranes have atendency to foul during processing. Fouling manifests itself as adecline in flux with time of operation. Flux decline is typically areduction in permeation flow or permeation rates that occurs when alloperating parameters, such as pressure, feed flow rate, temperature, andfeed concentration are kept constant. In general, membrane fouling is acomplicated process and is believed to occur due to a number of factorsincluding electrostatic attraction, hydrophobic and hydrophilicinteractions, the deposition and accumulation of feed components, e.g.,suspended particulates, impermeable dissolved solutes, and even normallypermeable solutes, on the membrane surface and/or within the pores ofthe membrane. It is expected that almost all feed components will foulmembranes to a certain extent. See Munir Cheryan, Ultrafiltration andMicrofiltration Handbook, Technical Publication, Lancaster, Pa., 1998(Pages 237-288). Fouling components and deposits can include inorganicsalts, particulates, microbials and organics.

Filtration membranes typically require periodic cleaning to allow forsuccessful industrial application within separation facilities such asthose found in the food, dairy, and beverage industries. The filtrationmembranes can be cleaned by removing foreign material from the surfaceand body of the membrane and associated equipment. The cleaningprocedure for filtration membranes can involve a clean-in-place CIPprocess where cleaning agents are circulated over the membrane to wet,penetrate, dissolve and/or rinse away foreign materials from themembrane. Various parameters that can be manipulated for cleaningtypically include time, temperature, mechanical energy, chemicalcomposition, chemical concentration, soil type, water type, hydraulicdesign, and membrane materials of construction.

Chemical energy in the form of detergents and cleaners can be used tosolubilize or disperse the foulant or soil. Thermal energy in the formof heat can be used to help the action of the chemical cleaners. Ingeneral, the greater the temperature of the cleaning the solution, themore effective it is as a cleaning treatment, although most membranematerials have temperature limitations due to the material ofconstruction. Many membranes additionally have chemical limitations.Mechanical energy in the form of high velocity flow also contributes tothe successful cleaning of membrane systems. See Munir Cheryan,Ultrafiltration and Microfiltration Handbook, Technical Publication,Lancaster, Pa., 1998, pages 237-288.

In general, the frequency of cleaning and type of chemical treatmentperformed on the membrane has been found to affect the operating life ofa membrane. It is believed that the operating life of a membrane can bedecreased as a result of chemical degradation of the membrane over time.Various membranes are provided having temperature, pH, and chemicalrestrictions to minimize degradation of the membrane material. Forexample, many polyamide reverse osmosis membranes have chlorinerestrictions because chlorine can have a tendency to oxidatively attackand damage the membrane. Cleaning and sanitizing filtration membranes isdesirable in order to comply with laws and regulations that may requirecleaning in certain applications (e.g., the food and biotechnologyindustries), reduce microorganisms to prevent contamination of theproduct streams, and optimize the process by restoring flux. See MunirCheryan, Ultrafiltration and Microfiltration Handbook, TechnicalPublication, Lancaster, Pa., 1998, pages 237-288.

Other exemplary techniques for cleaning filtration membranes aredisclosed by U.S. Pat. No. 4,740,308 to Fremont et al.; U.S. Pat. No.6,387,189 to Groschl et al.; U.S. Pat. No. 6,071,356 to Olsen; and MunirCheryan, Ultrafiltration and Microfiltration Handbook, TechnicalPublication, Lancaster, Pa., 1998 (Pages 237-239).

It is believed that membrane performance declines during processing ofmilk, whey, and other feed streams due to the fouling of the membranesurface or membrane pores by protein, fat, minerals, and other feedstream components.

The fouling of membranes processing high solid feed streams thereforerequire that they are cleaned regularly using a clean-in-place (CIP)approach in which the use of alkaline, acid, and cleaning adjuvants suchas surfactants and water conditioning polymers aid in the cleaning ofthe foulants and restore the membrane for functional use.

The proper use of alkaline, acid, and adjuvants requires anunderstanding of the functionality of the chemistry used. As an example,too high in pH or too low in pH can damage the polymeric membranematerial. The use of solvents or overuse of surfactants can often timelead to destruction of the glue line causing the membrane to delaminaterendering it non-functional. Overusing oxidative chemicals such assodium hypochlorite (chlorine bleach) or hydrogen peroxide canirreversibly damage some polymeric membrane types.

Conventional cleaning compositions used in CIP protocols, particularlythose intended for institutional use, often contain alkyl phenolethoxylates (APEs). APEs are used in cleaning compositions as a cleanserand a degreaser for their effectiveness at removing a variety of soilsfrom a variety of surfaces. Commonly used APEs include nonyl phenolethoxylates (NPE) surfactants such as NPE 9.5 or nonoxynol-9 which is a9.5 mole ethoxylate of nonyl phenol.

However, while effective, APEs are disfavored due to environmentalconcerns. For example, NPEs are formed through the combination ofethylene oxide with nonylphenol (NP). Both NP and NPEs exhibitestrogen-like properties and may contaminate water, vegetation andmarine life. NPE is also not readily biodegradable and remains in theenvironment or food chain for indefinite time periods. There istherefore a need in the art for an environmentally friendly andbiodegradable alternative that can replace APEs in membrane cleanerswhich allow membranes to be adequately cleaned from soils, do not causedamage to the membranes or membrane construction materials, and do notfoul the membranes themselves.

SUMMARY OF THE INVENTION

Disclosed herein are embodiments in the field of clean in place andother membrane cleaning protocols for cleaning membranes at separationfacilities. More specifically, the disclosure relates to a surfactantsystem that for use in the same that offers an environmentally saferalternative surfactant system than NPE which is currently used in manyoperations.

Disclosed herein is a surfactant system as well as alkaline cleaningcompositions incorporating the same and methods of use of the same. Inone embodiment, a surfactant system is disclosed for use alone or incleaning compositions. Applicants have identified characteristics andcertain extended nonionic surfactants for use in cleaning membranes.Disclosed herein is the use of one or more extended, nonionicsurfactants for membrane cleaning processes, also disclosed aresynergistic combinations of the same. In a preferred embodiment, thesurfactant is a branched extended chain propoxylated/ethoxylatedsurfactant. Additional characteristics of such surfactants are alsodisclosed. The surfactant in an embodiment has a cloud point of 50° C.or higher. Additional characteristics include a contact angle of below20°, on a polysulfone substrate and a low interfacial tension.Applicants have determined several surfactants and polymers, one or moreof which may be used successfully in membrane cleaning protocols. Insome embodiments the surfactant is a Guerbet alcohol.

Extended nonionic surfactants include those of the general formula:R-[L]x-[O—CH2-CH2]y

Where R is the lipophilic moiety, preferably branched, saturated orunsaturated, substituted or unsubstituted, aliphatic or aromatichydrocarbon radical having from about 8 to 20 carbon atoms, L is alinking group, block of poly-alkylene oxide, such as a block ofpoly-propylene oxide; x is the chain length of the linking group rangingfrom 5-25; and y is the average degree of ethoxylation ranging from1-20, preferably 6-10. Applicant has found that when L is PO thesuperior extension length is between 5 and 8 moles of PO.

Additional embodiments include combinations of extended chain nonionicsurfactants be used in combination with the preferred surfactants. Insome embodiments the surfactant has an R group of 2 ethyl, hexyl.

Another embodiment includes a cleaning composition comprising a sourceof alkalinity and the surfactant and/or polymer system. The source ofalkalinity is such that it comprises approximately 500 ppm to 10,000 ppmactives in a use solution. The surfactant system comprises from about0.05 weight percent to about 1.0 weight percent of actives in thecleaning solution. Additional functional ingredients such as chelants,preservatives, hydrotropes and the like may also be present. Thesurfactant system may be used as a part of a cleaning composition, maybe used as a booster composition in combination with standard cleaningcompositions, or may be used alone as part of an overall CIP process.

Another embodiment, is a method of removing soils, solutes and proteinsfrom filtration membranes in a cleaning process. The method includessteps of applying to a membrane the cleaning composition disclosedherein, in some embodiments the method includes removing liquid productfrom the filtration system, contacting the membrane with an alkalinecleaning composition, or surfactant system. In some embodiments themethod includes missing water with one of the surfactants disclosed andthereafter, flushing the membrane with water and the surfactantsdisclosed herein. This is typically achieved by circulating through thefiltration system with an aqueous cleaning use solution and thereafterrinsing the filtration system.

The membranes that can be treated include any membranes that aredesigned for periodic cleaning, and are often utilized in variousapplications requiring separation by filtration. Exemplary industriesthat utilize membranes that can be treated include the food industry,the beverage industry, the biotechnology industry, the pharmaceuticalindustry, the chemical industry, and the water purification industry. Inthe case of the food and beverage industries, products including milk,whey, fruit juice, beer, and wine are often processed through a membranefor separation. The water purification industry often relies uponmembranes for desalination, contaminant removal, and waste watertreatment. An exemplary use of membranes in the chemical industryincludes electropaint processes. The methods are particularly useful inremoving proteins, fats, and minerals, such as those from whey in a milkor cheese making process. In an embodiment the membrane is apolyethersulfone membrane, or a polyvinylidene fluoride membrane

While multiple embodiments are disclosed, still other will becomeapparent to those skilled in the art from the following detaileddescription, which shows and describes illustrative embodiments.Accordingly, the drawings and detailed description are to be regarded asillustrative in nature and not restrictive.

DESCRIPTION OF THE FIGURES

FIG. 1 is a graph of dynamic Interfacial Tension (IFT) measured at 50°C., 400 rpm against peanut oil.

FIG. 2 is a graph of dynamic IFT measured at 50° C., 400 rpm againstpalm oil.

FIG. 3 is a graph of dynamic IFT measured at 50° C., 400 rpm againstghee.

FIG. 4 is a graph of contact angle measured at 50° C. over time for EH 9surfactant, DI water, NPE and amine oxide.

FIG. 5 is a graph of contact angle for the surfactants EH9, 25R2, XP40and XP 80 at room temperature.

FIG. 6 is a graph of contact angle for the surfactants EH9, EH9/25R2,EH9/XP40 and EH9/XP80 at 95/5 blend at room temperature.

FIG. 7 is a graph of contact angle for the surfactants EH9, EH9/25R2,EH9/XP40 and EH9/XP80 at 90/10 blend at room temperature.

FIG. 8 is a graph of contact angle for the surfactants EH9, EH9/25R2,EH9/XP40 and EH9/XP80 at 80/20 blend at room temperature.

FIG. 9 is a contact angle comparison of EH9 and XP40 blends onpolysulfone coupon at room temperature.

FIG. 10 is an interfacial tension against ghee of surfactants at 1000ppm, pH 11, and 50° C.

FIG. 11 is a graph of butterfat removal of various EH9/XP40 blends.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients or reaction conditions usedherein are to be understood as being modified in all instances by theterm “about”.

As used herein, weight percent (wt-%), percent by weight, % by weight,and the like are synonyms that refer to the concentration of a substanceas the weight of that substance divided by the total weight of thecomposition and multiplied by 100.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions disclosed or employed in the methods disclosedrefers to variation in the numerical quantity that can occur, forexample, through typical measuring and liquid handling procedures usedfor making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term about alsoencompasses amounts that differ due to different equilibrium conditionsfor a composition resulting from a particular initial mixture. Whetheror not modified by the term “about,” the claims include equivalents tothe quantities.

The term “alkyl” or “alkyl groups,” as used herein, refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups. In some embodiments, substitutedalkyls can include a heterocyclic group. As used herein, the term“heterocyclic group” includes closed ring structures analogous tocarbocyclic groups in which one or more of the carbon atoms in the ringis an element other than carbon, for example, nitrogen, sulfur oroxygen. Heterocyclic groups may be saturated or unsaturated. Exemplaryheterocyclic groups include, but are not limited to, aziridine, ethyleneoxide (epoxides, oxiranes), thiirane (episulfides), dioxirane,azetidine, oxetane, thietane, dioxetane, dithietane, dithiete,azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

The term “surfactant” or “surface active agent” refers to an organicchemical that when added to a liquid changes the properties of thatliquid at a surface.

“Cleaning” means to perform or aid in soil removal, bleaching, microbialpopulation reduction, rinsing, or combination thereof.

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the effectiveness of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt. %. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt. %.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the terms “alkyl phenol ethoxylate-free” or “NPE-free”refers to a composition, mixture, or ingredients that do not containalkyl phenol ethoxylates or phenol-containing compounds or to which thesame has not been added. Should alkyl phenol ethoxylates or—alkyl phenolethoxylate containing compound be present through contamination of acomposition, mixture, or ingredients, the amount of the same shall beless than 0.5 wt. %. In another embodiment, the amount of is less than0.1 wt-% and in yet another embodiment, the amount is less than 0.01 wt.%.

The term “substantially similar cleaning performance” refers generallyto achievement by a substitute cleaning product or substitute cleaningsystem of generally the same degree (or at least not a significantlylesser degree) of cleanliness or with generally the same expenditure (orat least not a significantly lesser expenditure) of effort, or both,when using the substitute cleaning product or substitute cleaning systemrather than a alkyl phenol ethoxylate-containing cleaning to address atypical soiling condition on a typical substrate. This degree ofcleanliness may, depending on the particular cleaning product andparticular substrate, correspond to a general absence of visible soils,or to some lesser degree of cleanliness, as explained in the priorparagraph.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5).

The terms “include” and “including” when used in reference to a list ofmaterials refer to but are not limited to the materials so listed.

Surfactant/Polymer System

The disclosure includes a surfactant system which can be used as abooster or as part of an alkaline or acid cleaning composition andmethods of use of the same. The surfactants can be used as a membranecleaning adjuvant for improved removal of proteins, fat, and other soilsfrom membranes and in some cases improving the hydrophilicity propertiesof membranes and improve processing permeation properties. Otherconsiderations for a successful surfactant system include good rinsingcharacteristics, low foaming, good soil removal or cleaning properties,biodegradability, and relatively low cost. The use of a membraneincompatible surfactant can cause fouling issues on membrane surfaces.For example, the use of cationic surfactants are often associated withirreversible fouling of the membrane due to the inability to rinse orwash the surfactant from the surface. It is understood that the membranehas a negative surface charge and therefore a cationic surfactant isstrongly attracted to the surface and cannot be easily removed. Thisresidual surfactant on the surface acts as a foulant causing lowproduction and water flux rates resulting in poor productionperformance.

Other surfactants such as anionic surfactants (DDBSA) are not attractedto the surface due to both the membrane and surfactant being negativelycharged. This is believed to improve the rinseability of the surfactantwhile allowing it to assist in the aid of cleaning fats and proteins dueto its reduction in surface tension.

Nonionic surfactants have been sparingly used as membrane cleaningadjuvants. They typically have positive properties such as degreasing,low foaming, wetting, and reducing surface tension. However, many of thenonionic surfactants can also cause fouling problems to the membrane dueto their general poor rinseability characteristics. As the nonionics aretechnically neutral molecules, the predictability of whether or not theywill perform well as a surfactant booster on a particular membrane typeis less certain. Molecular weight, hydrophilic-lipophilic-balance (HLB),alcohol chain length, Draves wetting, and degree of ethoxylation alonedo not adequately predict whether or not a nonionic surfactant orpolymer will function well on a membrane. Applicants have discoveredthat when using extended chain nonionic surfactants several importantcharacteristics, do exist and should be considered. For example, contactangle as a predictor of wettability is important, and it is preferredthat the contact angle be less than 20 degrees on the membranesubstrate. Also important is branching, in that at least some branchingtends to improve cleaning characteristics. A low surfactant interfacialtension is perhaps the most important predictor as well as a cloud pointthat is near or higher than the cleaning temperature (typically 50° C.or higher).

In addition, the membrane surface type such as polyethersulfone (PES),polyvinylidenedifluoride (PVDF) have different surface energies thatalso affect how a surfactant functions on the surface and how thefoulant functions on the surface. The molecular weight cut-off or poresize of a particular membrane will also likely affect the functionalityof a surfactant due to pore fouling, pore penetration for cleaningpores, membrane permeation exclusion due to branching and molecularweight, and ease of permeation due to linearity.

One embodiment includes a surfactant component for use in the cleaningcompositions and methods. The surfactant and polymer component ispreferably a nonionic extended chain PO/EO surfactant.

Surfactants/Polymers

In certain embodiments, the surfactant includes one or more nonionicsurfactants generally characterized by the presence of an organichydrophobic group and an organic hydrophilic group and are typicallyproduced by the condensation of an organic aliphatic, alkyl aromatic orpolyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxidemoiety which in common practice is ethylene oxide or a polyhydrationproduct thereof, polyethylene glycol. Practically any hydrophobiccompound having a hydroxyl, carboxyl, amino, or amido group with areactive hydrogen atom can be condensed with ethylene oxide, or itspolyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties.

Disclosed herein is the use of one or more extended, nonionicsurfactants for membrane cleaning processes. In a preferred embodiment,the surfactant is an extended chain branched ethoxylated/propoxylatedalcohol. The surfactant in an embodiment has a cloud point of 50° orhigher. Additional characteristics include a contact angle of below 20,and a low interfacial tension. Applicants have determined severalsurfactants and polymers, one or more of which may be used successfullyin membrane cleaning protocols.Extended nonionic surfactants include those of the general formula:R-[L]x-[O—CH2-CH2]y

Where R is the lipophilic moiety, preferably branched, saturated orunsaturated, substituted or unsubstituted, aliphatic or aromatichydrocarbon radical having from about 8 to 20 carbon atoms, L is alinking group, block of poly-alkylene oxide, such as a block ofpoly-propylene oxide, a block of poly-ethylene oxide, a block ofpoly-butylene oxide or a mixture thereof; x is the chain length of thelinking group ranging from 5-25; and y is the average degree ofethoxylation ranging from 1-20. Applicant has found that when L is POthe superior extension length is between 5 and 8 moles of PO.

Another embodiment is to provide a cleaning composition comprising asource of alkalinity and the surfactant system. The source of alkalinityis such that it comprises approximately 500 ppm to 10,000 ppm actives ina use solution. The surfactant system comprises from about 0.05 weightpercent to about 1.0 weight percent of actives in the cleaning solution.Additional functional ingredients such as chelants, preservatives,hydrotropes and the like may also be present. The surfactant system maybe used as a part of a cleaning composition, may be used as a boostercomposition in combination with standard cleaning compositions, or maybe used alone as part of an overall CIP process.

Preferred extended surfactants include: branched Guerbet alcoholalkoxylates; such as C₁₀(PO)₈(EO)_(x) (x=3, 6, 8, 10) also, extendedlinear alcohol alkoxylates; C₍₁₂₋₁₄₎(PO)₁₆(EO)_(x) (x=6, 12, 17).

Branched Alcohol Alkoxylates

Preferred branched alcohol alkoxylates include Guerbet ethoxylates.Guerbet ethoxylates suitable have the following formula:

The Guerbet ethoxylate may be further defined wherein R1 is C2-C20 alkyland R2 is H or C1-C4 alkyl. In a further aspect, the Guerbet ethoxylateis defined wherein “n” is an integer between 2 and 20 and wherein “m” isan integer between 1 and 40.

In a preferred aspect, the branched alcohol alkoxylate is a Guerbetethoxylate that is prepared from a Guerbet alcohol by dimerization ofalkenes (e.g. butane).

The branched alcohol alkoxylates, including Guerbet ethoxylates, can beprepared according to U.S. Pat. Nos. 6,906,320, 6,737,553 and 5,977,048,the disclosure of these patents are herein incorporated by reference intheir entirety. Exemplary branched alcohol alkoxylates include thoseavailable under the tradenames Lutensol XP-30 and Lutensol XP-50 (BASFCorporation). In general, Lutensol XP-30 can be considered to have 3repeating ethoxy groups, and Lutensol XP-50 can be considered to have 5repeating ethoxy groups.

Branched alcohol alkoxylates can be classified as relatively waterinsoluble or relatively water soluble. In general, a water insolublebranched alcohol alkoxylate can be considered an alkoxylate that, whenprovided as a composition containing 5 wt.-% of the branched alcoholalkoxylate and 95 wt.-% water, has a tendency to phase separate.Lutensol XP-30 and Lutensol XP-50 from BASF Corporation are examples ofwater-insoluble branched alcohol alkoxylates.

According to an embodiment a branched alcohol alkoxylate, preferably awater-insoluble Guerbet ethoxylate has from about 10 wt.-% to about 90wt.-% ethylene oxide, from about 20 wt.-% to about 70 wt.-% ethyleneoxide preferably from about 30 wt.-% to about 60 wt.-% ethylene oxide.In a preferred embodiment these surfactants may be used in combinationwith other surfactants, such as the Ethyl hexyl (PO)5(EO)y extendedsurfactants.

Additional extended surfactants include capped extended nonionicsurfactants which lower the foam profile of the composition and foamfrom protein soil.

Capped extended nonionic surfactants can include:R—[PO]_(x)-[EO]_(y)[N]z

Where N is a capping group such as an alkyl group such as methyl,benzyl, butyl, etc.; a PO group of from 1-5 length, in length. Thesecapped nonionic surfactants have lowered foam profiles and the like areeffective for rinse aid formulations and detergents.

Many extended chain anionic and nonionic surfactants are commerciallyavailable from a number of sources. Table 1 is a representative,nonlimiting listing of several examples of the same.

TABLE 1 Extended % Surfactants Source Active Structure Plurafac SL- BASF100 C6-10-(PO)3(EO)6 42(nonionic) Plurafac SL- BASF 100 C6-10-(PO)3(EO)862(nonionic) Lutensol XP- BASF 100 (3 propyl heptanol 40(nonionic)Guerbet alcohol series) C10-(PO)a(EO)b series, where a is 1.0 to 1.5,and b is 4 to 14. Lutensol XP- BASF 100 50(nonionic) Lutensol XP- BASF100 60(nonionic) Lutensol XP- BASF 100 69(nonionic) Lutensol XP- BASF100 70(nonionic) Lutensol XP- BASF 85 79(nonionic) Lutensol XP- BASF 10080(nonionic) Lutensol XP- BASF 80 89(nonionic) Lutensol XP-90 BASF 100(nonionic) Lutensol XP-99 BASF 80 (nonionic) Lutensol XL-100 BASF 100(nonionic) Lutensol XP-140 BASF 100 (nonionic) New Lutensol XL BASF 100C10 Guerbet alcohol surfactant designed (PO)8(EO)3 by Ecolab NewLutensol XL BASF 100 C10 Guerbet alcohol surfactant designed (PO)8(EO)6by Ecolab New Lutensol XL BASF 100 C10 Guerbet alcohol surfactantdesigned (PO)8(EO)8 by Ecolab New Lutensol XL BASF 100 C10 Guerbetalcohol surfactant designed (PO)8(EO)10 by Ecolab Ecosurf EH-3 Dow 1002-Ethyl Hexyl (nonionic) (PO)₅(EO)_(3, 6, or 9) Ecosurf EH-6 Dow 100series (nonionic) Ecosurf EH- Dow 100 9(nonionic) Ecosurf SA- Dow 100 C6-12 (PO)3-4 4(nonionic) (EO)4 Ecosurf SA-7 Dow 100 C 6-12 (PO) 3-4(nonionic) (EO)7 Ecosurf SA-9 Dow 100 C 6-12 (PO) 3-4 (nonionic) (EO)9Surfonic PEA- Huntsman 100 C12- 25(nonionic) 14(PO)2N[(EO)2.5}2 X-AES(anionic) Huntsman 23 C12-14-(PO)16- (EO)2-sulfate X-LAE6 (nonionic)Huntsman 100 C 12-14- (PO)16(EO)6 X-LAE12 (nonionic) Huntsman 100 C12-14- (PO)16(EO)12 X-LAE17 (nonionic) Huntsman 100 C 12-14-(PO)16(EO)17 Alfoterra 123-4S Sasol 30 C 12-13-(PO)4- (anionic) sulfateAlfoterra 123-8S Sasol 30 C 12-13-(PO)8- (anionic) sulfate Marlowet 4561Sasol 90 C16-18(PO)4(EO)5- (nonionic under carboxylic acid acidiccondition, anionic under alkaline condition) Marlowet 4560 Sasol 90C16-18(PO)4(EO)2- (nonionic under carboxylic acid acidic condition,anionic under alkaline condition) Marlowet 4539 Sasol 90 IsoC9-(PO)2EO2- (nonionic under carboxylic acid acidic condition, anionicunder alkaline condition) LP-6818-41-IP2 Exp 100 C 12-14-(PO)4LP-6818-41-IP3 Exp 100 C 12-14-(PO)6 LP-6818-41-IP4 Exp 100 C12-14-(PO)8 LP-6818-47-IP5 Exp 100 C 12-14- (PO)4(EO)12 LP-6818-47-IP6Exp 100 C 12-14- (PO)4(EO)14 LP-6818-47-IP7 Exp 100 C 12-14- (PO)4(EO)16LP-6818-49-FB Exp 100 C 12-14- (PO)4(EO)18 LP-6818-51-IP1 Exp 100 C12-14- (PO)6(EO)14 LP-6818-51-IP2 Exp 100 C 12-14- (PO)6(EO)16LP-6818-53-IP3 Exp 100 C 12-14- (PO)6(EO)18 LP-6818-53-FB Exp 100 C12-14- (PO)6(EO)20 LP-6818-66-IP2 Exp 100 TDA-(PO)4 LP-6818-67-IP3 Exp100 TDA-(PO)4(EO)8 LP-6818-67-IP4 Exp 100 TDA-(PO)4(EO)10 LP-6818-67-IP5Exp 100 TDA-(PO)4(EO)12 LP-6818-68-IP5 LP-6818-68-IP6 Exp 100TDA-(PO)4(EO)14 LP-6818-68-FB Exp 100 TDA-(PO)4(EO)18 Exp 100 C 12-14-(PO)20(EO)2 Exp 100 C 12-14- (PO)20(EO)4 Exp 100 C 12-(PO)20(EO)6 Isofol12 PO5EO5 Exp 100 Guerbet C 12- (PO)5(EO)5 Isofol 12 PO5EO8 Exp 100Guerbet C 12- (PO)5(EO)8 Isofol 12 PO8EO5 Exp 100 Guerbet C 12-(PO)8(EO)5 Isofol 12 PO8EO8 Exp 100 Guerbet C 12- (PO)8(EO)8 Capped DOW100 C 8-10- Triton DF-12 (PO)2(EO)11-Benzyl Plurafac SLF-180 BASF 100C10 Guerbet alcohol (PO)3(EO)10(PO)10 ** Exp are manufactured by EcolabParticularly preferred are branched Ethyl Hexyl (PO)₅(EO)_(6 or 9)extended nonionic surfactants. More preferably branched at position 2.In additional embodiments, the branched ethyl hexyl extended alcohol maybe paired with a Guerbet alcohol, such as the Lutensol series ofsurfactants from BASF. (3 propyl heptanol Guerbet alcohol C10-(PO)a(EO)bseries, where a is 1.0 to 1.5, and b is 4 to 14). The surfactant systemmay be used alone as a booster, comprising surfactant and a carrier,(such as water) or may comprise from about 0.005 weight percent to about5.0 weight percent of actives, preferably about 0.01 weight percent toabout 3.0 weight percent, and more preferably about 0.05 weight percentto about 1.0 weight percent actives as part of a cleaning composition.

Additional Nonionic Surfactant

In certain embodiments, additional nonionic surfactants may be used in acleaning composition along with the surfactants disclosed. Usefulnonionic surfactants include:

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from 6 to 24 carbon atoms withfrom 3 to 50 moles of ethylene oxide. The alcohol moiety can consist ofmixtures of alcohols in the above delineated carbon range or it canconsist of an alcohol having a specific number of carbon atoms withinthis range. Examples of like commercial surfactant are available underthe trade names Neodol® manufactured by Shell Chemical Co. and Alfonic®manufactured by Vista Chemical Co. This includes Guerbet alcohols suchas those sold under the Lutensol name from BASF.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application herein. All of these estermoieties have one or more reactive hydrogen sites on their moleculewhich can undergo further acylation or ethylene oxide (alkoxide)addition to control the hydrophilicity of these substances.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₁₀-C₁₈ ethoxylatedfatty alcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from 6 to 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing from1.3 to 10 saccharide units. Any reducing saccharide containing 5 or 6carbon atoms can be used, e.g., glucose, galactose and galactosylmoieties can be substituted for the glucosyl moieties. (Optionally thehydrophobic group is attached at the 2-, 3-, 4-, etc. positions thusgiving a glucose or galactose as opposed to a glucoside or galactoside.)The intersaccharide bonds can be, e.g., between the one position of theadditional saccharide units and the 2-, 3-, 4-, and/or 6-positions onthe preceding saccharide units.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed. A typical listing of nonionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).

In some embodiments the non-ionic surfactant is a Guerbet alcoholethoxylate of the formula R¹—(OC₂H₄)_(n)—(OH), wherein IV is a branchedC₉-C₂₀ alkyl group and n is from 2 to 10.

In a preferred embodiment the Guerbet alcohol ethoxylate being used inthe liquid surfactant system is a Guerbet alcohol ethoxylate of theformula R¹—(OC₂H₄)_(n)—(OH), This includes a Guerbet alcohol ethoxylatewhere R¹ is a branched C₁₀ to C₁₈ alkyl group and n is from 5 to 10,preferably 7 to 9 and also ones wherein R¹ is C₈ to C₁₂ branched alkylgroup, preferably branched C₁₀ alkyl group and n is 2 to 4, preferably3. Such Guerbet alcohols are available, for example, under the tradename Lutensol from BASF or Eutanol G from Cognis.

The Guerbet reaction is a self-condensation of alcohols by whichalcohols having branched alkyl chains are produced. The reactionsequence is related to the Aldol condensation and occurs at hightemperatures under catalytic conditions. The product is a branchedalcohol with twice the molecular weight of the reactant minus a mole ofwater. The reaction proceeds by a number of sequential reaction steps.At first the alcohol is oxidised to an aldehyde. Then Aldol condensationtakes place after proton extraction. Thereafter the aldol product isdehydrated and the hydrogenation of the allylic aldehyde takes place.

These products are called Guerbet alcohols and are further reacted tothe non-ionic alkoxylated Guerbet alcohols by alkoxylation with i.e.ethylene oxide or propylene oxide. The ethoxylated Guerbet alcohols havea lower solubility in water compared to the linear ethoxylated alcoholswith the same number of carbon atoms. Therefore the exchange of linearfatty alcohols by branched fatty alcohols makes it necessary to use goodsolubilizers which are able to keep the guerbet alcohol in solution andthe resulting emulsion stable even over a longer storage time.

In certain embodiments the surfactant systems include one or more othersuitable polymers which may be used such as alkyl aryl sulfonates.Suitable alkyl aryl sulfonates that can be used in the cleaningcomposition can have an alkyl group that contains 6 to 24 carbon atomsand the aryl group can be at least one of benzene, toluene, and xylene.A suitable alkyl aryl sulfonate includes linear alkyl benzene sulfonate.A suitable linear alkyl benzene sulfonate includes linear dodecyl benzylsulfonate that can be provided as the sulfonic acid that is neutralizedto form the sulfonate. Additional suitable alkyl aryl sulfonates includexylene sulfonate and cumene sulfonate.

Suitable alkane sulfonates that can be used in the cleaning compositioncan have an alkane group having 6 to 24 carbon atoms. Suitable alkanesulfonates that can be included are secondary alkane sulfonates. Asuitable secondary alkane sulfonate includes sodium C₁₄-C₁₇ secondaryalkyl sulfonate commercially available as Hostapur SAS from Clariant.

In a preferred embodiment the surfactant system includes one or more ofthe following: a polyalkylene glycol, an ethoxylated alcohol, apolyalkylene glycol ether ethoxylate, an alkyl glucoside, an alkyl arylsulfonate, an alkyl dimethyl amine oxide, and an alpha olefin sulfonate.In a more preferred embodiment the surfactant includes a polyethyleneglycol, a linear C9-C11 alcohol ethoxylate, (preferably with 5-6 molesof ethoxylation, a Guerbet alcohol alkoxylate, such as those sold underthe tradename Lutensol® (ex. BASF AG), available in a variety of grades,preferably Lutensol XP-50, a hexyl alkyl glucoside, a linear alkylbenzene sulfonate, a lauryl dimethyl amine oxide, and an alpha olefinsulfonate.

Water

The booster and cleaning compositions may comprise water in amounts thatvary depending upon techniques for processing the composition.

Water provides a medium which dissolves, suspends, or carries the othercomponents of the composition. Water can also function to deliver andwet the composition on an object.

In some embodiments, water makes up a large portion of the compositionand may be the balance of the composition apart from surfactant blend,source of alkalinity, additional ingredients, and the like. The wateramount and type will depend upon the nature of the composition as awhole, the environmental storage, and method of application includingconcentration composition, form of the composition, and intended methodof delivery, among other factors. Notably the carrier should be chosenand used at a concentration which does not inhibit the efficacy of thefunctional components in the composition for the intended use, e.g.,bleaching, sanitizing, cleaning.

In certain embodiments, the present composition includes about 5 toabout 90 wt.-% water, about 10 to about 80 wt. % water, about 20 toabout 60 wt % water, or about 30 to about 40 wt % water. It is to beunderstood that all values and ranges between these values and rangesare encompassed herein.

Cleaning Compositions

As indicated earlier, the surfactant blend of the composition may beformulated as part of a cleaning composition including a source ofalkalinity and/or acid.

Source of Alkalinity

The cleaning composition includes an effective amount of one or morealkaline sources to enhance cleaning and improve soil removalperformance. In general, it is expected that a concentrated cleaningcomposition will include the alkaline source in an amount of at leastabout 5% by weight, at least about 10% by weight, at least about 15% byweight, or at least about 25% by weight. In order to provide sufficientroom for other components in the concentrate, the alkaline source can beprovided in the concentrate in an amount of less than about 75% byweight, less than about 60% by weight, or less than about 50% by weight.In another embodiment, the alkalinity source may constitute betweenabout 0.1% and about 90% by weight, between about 0.5% and about 80% byweight, and between about 1% and about 60% by weight of the total weightof the cleaning composition. A source of alkalinity is present in anamount sufficient to provide 500 ppm to about 5000 ppm actives in a usecomposition.

An effective amount of one or more alkaline sources should be consideredas an amount that provides a use composition having a pH of at leastabout 8 and usually between about 9.5 and 13. When the use compositionhas a pH of between about 8 and about 10, it can be considered mildlyalkaline, and when the pH is greater than about 13, the use compositioncan be considered caustic. In some circumstances, the cleaningcomposition may provide a use composition that is useful at pH levelsbelow about 8. In such compositions, the alkaline source may be omitted,and additional pH adjusting agents may be used to provide the usecomposition with the desired pH.

Examples of suitable alkaline sources of the cleaning compositioninclude, but are not limited to alkali metal carbonates and alkali metalhydroxides. Exemplary alkali metal carbonates that can be used include,but are not limited to: sodium or potassium carbonate, bicarbonate,sesquicarbonate, and mixtures thereof. Exemplary alkali metal hydroxidesthat can be used include, but are not limited to sodium, lithium, orpotassium hydroxide. The alkali metal hydroxide may be added to thecomposition in any form known in the art, including as solid beads,dissolved in an aqueous solution, or a combination thereof. Alkali metalhydroxides are commercially available as a solid in the form of prilledsolids or beads having a mix of particle sizes ranging from about 12-100U.S. mesh, or as an aqueous solution, as for example, as a 45% and a 50%by weight solution. In one embodiment, the alkali metal hydroxide isadded in the form of an aqueous solution, particularly a 50% by weighthydroxide solution, to reduce the amount of heat generated in thecomposition due to hydration of the solid alkali material.

In addition to the first alkalinity source, the cleaning composition maycomprise a secondary alkalinity source. Examples of useful secondaryalkaline sources include, but are not limited to: metal silicates suchas sodium or potassium silicate or metasilicate; metal carbonates suchas sodium or potassium carbonate, bicarbonate, sesquicarbonate;

metal borates such as sodium or potassium borate; and ethanolamines andamines. Such alkalinity agents are commonly available in either aqueousor powdered form, either of which is useful in formulating the presentcleaning compositions.

The cleaning composition may be phosphorus-free and/or nitrilotriaceticacid (NTA)-free to meet certain regulations. Phosphorus-free (alsoreferred to as “free of phosphorous”) means a concentrated compositionhaving less than approximately 0.5 wt %, more particularly, less thanapproximately 0.1 wt %, and even more particularly less thanapproximately 0.01 wt % phosphorous based on the total weight of theconcentrated composition. NTA-free (also referred to as “free of NTA”)means a concentrated composition having less than approximately 0.5 wt%, less than approximately 0.1 wt %, and often less than approximately0.01 wt % NTA based on the total weight of the concentrated composition.

Source of Acidity

The compositions can also be acidic in nature and can comprise at leastone inorganic and/or organic acid in a sufficient amount in order thatthe compositions have a pH of 4 or less. Generally, useful inorganicacids include water soluble inorganic and mineral acids. Non-limitingexamples of useful acids include hydrochloric acid, phosphoric acid,sulfuric acid, and so forth individually or in combination.

As for organic acids, non-limiting examples include any known organicacid which may be found effective in the inventive compositions.Generally useful organic acids are those which include at least onecarbon atom, and include at least one carboxyl group (—COOH) in itsstructure. More specifically, useful organic acids contain from 1 toabout 6 carbon atoms, have at least one carboxyl group, and are watersoluble. Non-limiting examples include acetic acid, chloroacetic acid,citric acid, formic acid, propionic acid, and so forth.

Additional Functional Materials

The components of the surfactant booster or cleaning composition can becombined with various additional functional components. In someembodiments, the cleaning composition including the alkalinity source,acidity source, the surfactant system, and water make up a large amount,or even substantially all of the total weight of the cleaningcomposition, for example, in embodiments having few or no additionalfunctional materials disposed therein. In these embodiments, thecomponent concentrations ranges provided above for the cleaningcomposition are representative of the ranges of those same components inthe cleaning composition.

The functional materials provide desired properties and functionalitiesto the detergent composition. For the purpose of this application, theterm “functional materials” includes a material that when dispersed ordissolved in a use and/or concentrate, such as an aqueous solution,provides a beneficial property in a particular use. Some particularexamples of functional materials are discussed in more detail below,although the particular materials discussed are given by way of exampleonly, and that a broad variety of other functional materials may beused. For example, many of the functional materials discussed belowrelate to materials used in cleaning applications. However, otherembodiments may include functional materials for use in otherapplications.

Additional Surfactants

The cleaning composition can contain an additional surfactant componentthat includes a detersive amount of an anionic surfactant or a mixtureof anionic surfactants. Anionic surfactants are desirable in cleaningcompositions because of their wetting, detersive properties, and oftentimes good compatibility with membranes. The anionic surfactants thatcan be used include any anionic surfactant available in the cleaningindustry. Suitable groups of anionic surfactants include sulfonates andsulfates. Suitable surfactants that can be provided in the anionicsurfactant component include alkyl aryl sulfonates, secondary alkanesulfonates, alkyl methyl ester sulfonates, alpha olefin sulfonates,alkyl ether sulfates, alkyl sulfates, and alcohol sulfates.

Suitable alkyl aryl sulfonates that can be used in the cleaningcomposition can have an alkyl group that contains 6 to 24 carbon atomsand the aryl group can be at least one of benzene, toluene, and xylene.A suitable alkyl aryl sulfonate includes linear alkyl benzene sulfonate.A suitable linear alkyl benzene sulfonate includes linear dodecyl benzylsulfonate that can be provided as an acid that is neutralized to formthe sulfonate. Additional suitable alkyl aryl sulfonates include xylenesulfonate and cumene sulfonate.

Suitable alkane sulfonates that can be used in the cleaning compositioncan have an alkane group having 6 to 24 carbon atoms. Suitable alkanesulfonates that can be used include secondary alkane sulfonates. Asuitable secondary alkane sulfonate includes sodium C₁₄-C₁₇ secondaryalkyl sulfonate commercially available as Hostapur SAS from Clariant.

Suitable alkyl methyl ester sulfonates that can be used in the cleaningcomposition include those having an alkyl group containing 6 to 24carbon atoms. Suitable alpha olefin sulfonates that can be used in thecleaning composition include those having alpha olefin groups containing6 to 24 carbon atoms.

Suitable alkyl ether sulfates that can be used in the cleaningcomposition include those having between about 1 and about 10 repeatingalkoxy groups, between about 1 and about 5 repeating alkoxy groups. Ingeneral, the alkoxy group will contain between about 2 and about 4carbon atoms. A suitable alkoxy group is ethoxy. A suitable alkyl ethersulfate is sodium lauryl ether ethoxylate sulfate and is available underthe name Steol CS-460.

Suitable alkyl sulfates that can be used in the cleaning compositioninclude those having an alkyl group containing 6 to 24 carbon atoms.Suitable alkyl sulfates include, but are not limited to, sodium laurylsulfate and sodium lauryl/myristyl sulfate.

Suitable alcohol sulfates that can be used in the cleaning compositioninclude those having an alcohol group containing about 6 to about 24carbon atoms.

In a preferred embodiment, the co-surfactant component is a smallerchain material, preferably less than 12 carbons and most preferably fromabout 6 to about 10 carbons. The surfactant and any optionalco-surfactant combination together replace NPE on a 1:1 basis at theactives level.

The anionic surfactant can be neutralized with an alkaline metal salt,an amine, or a mixture thereof. Suitable alkaline metal salts includesodium, potassium, and magnesium. Suitable amines includemonoethanolamine, triethanolamine, and monoisopropanolamine. If amixture of salts is used, a suitable mixture of alkaline metal salt canbe sodium and magnesium, and the molar ratio of sodium to magnesium canbe between about 3:1 and about 1:1.

The cleaning composition, when provided as a concentrate, can includethe surfactant component in an amount sufficient to provide a usecomposition having desired wetting and detersive properties afterdilution with water. The concentrate can contain about 0.1 wt. % toabout 0.5 wt. %, about 0.1 wt. % to about 1.0 wt. %, about 1.0 wt. % toabout 5 wt. %, about 5 wt. % to about 10 wt. %, about 10 wt. % to about20 wt. %, 30 wt. %, about 0.5 wt. % to about 25 wt. %, and about 1 wt. %to about 15 wt. %, and similar intermediate concentrations of theanionic surfactant.

The cleaning composition can contain an additional nonionic cosurfactantcomponent that includes a detersive amount of an additional nonionicsurfactant or a mixture of nonionic surfactants. Nonionic cosurfactantscan be included in the cleaning composition to enhance grease removalproperties. Although the additional cosurfactant component can include anonionic surfactant component, it should be understood that the nonioniccosurfactant component can be excluded from the cleaning composition.

Nonionic cosurfactants that can be used in the composition includepolyalkylene oxide surfactants (also known as polyoxyalkylenesurfactants or polyalkylene glycol surfactants). Suitable polyalkyleneoxide surfactants include polyoxypropylene surfactants andpolyoxyethylene glycol surfactants. Suitable surfactants of this typeare synthetic organic polyoxypropylene (PO)-polyoxyethylene (EO) blockcopolymers. These surfactants include a di-block polymer comprising anEO block and a PO block, a center block of polyoxypropylene units (PO),and having blocks of polyoxyethylene grafted onto the polyoxypropyleneunit or a center block of EO with attached PO blocks. Further, thissurfactant can have further blocks of either polyoxyethylene orpolyoxypropylene in the molecules. A suitable average molecular weightrange of useful surfactants can be about 1,000 to about 40,000 and theweight percent content of ethylene oxide can be about 10-80 wt. %.

Additional nonionic cosurfactants include alcohol alkoxylates. Asuitable alcohol alkoxylate include linear alcohol ethoxylates such asTomadol™ 1-5 which is a surfactant containing an alkyl group having 11carbon atoms and 5 moles of ethylene oxide. Additional alcoholalkoxylates include alkylphenol ethoxylates, branched alcoholethoxylates, secondary alcohol ethoxylates (e.g., Tergitol 15-S-7 fromDow Chemical), castor oil ethoxylates, alkylamine ethoxylates, tallowamine ethoxylates, fatty acid ethoxylates, sorbital oleate ethoxylates,end-capped ethoxylates, or mixtures thereof. Additional nonionicsurfactants include amides such as fatty alkanolamides,alkyldiethanolamides, coconut diethanolamide, lauramide diethanolamide,cocoamide diethanolamide, polyethylene glycol cocoamide (e.g., PEG-6cocoamide), oleic diethanolamide, or mixtures thereof. Additionalsuitable nonionic surfactants include polyalkoxylated aliphatic base,polyalkoxylated amide, glycol esters, glycerol esters, amine oxides,phosphate esters, alcohol phosphate, fatty triglycerides, fattytriglyceride esters, alkyl ether phosphate, alkyl esters, alkyl phenolethoxylate phosphate esters, alkyl polysaccharides, block copolymers,alkyl glucosides, or mixtures thereof.

When nonionic cosurfactants are included in the cleaning compositionconcentrate, they can be included in an amount of at least about 0.1 wt.% and can be included in an amount of up to about 15 wt. %. Theconcentrate can include about 0.1 to 1.0 wt. %, about 0.5 wt. % to about12 wt. % or about 2 wt. % to about 10 wt. % of the nonionic surfactant.

Amphoteric surfactants can also be used to provide desired detersiveproperties. Suitable amphoteric surfactants that can be used include,but are not limited to: betaines, imidazolines, and propionates.Suitable amphoteric surfactants include, but are not limited to:sultaines, amphopropionates, amphodipropionates, aminopropionates,aminodipropionates, amphoacetates, amphodiacetates, andamphohydroxypropylsulfonates.

When the cleaning composition includes an amphoteric surfactant, theamphoteric surfactant can be included in an amount of about 0.1 wt. % toabout 15 wt. %. The concentrate can include about 0.1 wt. % to about 1.0wt. %, 0.5 wt. % to about 12 wt. % or about 2 wt. % to about 10 wt. % ofthe amphoteric surfactant.

Bleaching Agents

The cleaning composition may also include bleaching agents forlightening or whitening a substrate. Examples of suitable bleachingagents include bleaching compounds capable of liberating an activehalogen species, such as Cl₂, Br₂, —OCl⁻ and/or —OBr⁻, under conditionstypically encountered during the cleansing process. Suitable bleachingagents for use in the present cleaning compositions include, forexample, chlorine-containing compounds such as a chlorine, ahypochlorite, and chloramine. Exemplary halogen-releasing compoundsinclude the alkali metal dichloroisocyanurates, chlorinated trisodiumphosphate, the alkali metal hypochlorites, monochloroamine anddichloroamine, and the like. Encapsulated chlorine sources may also beused to enhance the stability of the chlorine source in the composition(see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773, thedisclosures of which are incorporated by reference herein for allpurposes). A bleaching agent may also be a peroxygen or active oxygensource such as hydrogen peroxide, perborates, sodium carbonateperoxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, andsodium perborate mono and tetrahydrate, with and without activators suchas tetraacetylethylene diamine, and the like. The composition caninclude an effective amount of a bleaching agent. When the concentrateincludes a bleaching agent, it can be included in an amount of about 0.1wt. % to about 60 wt. %, about 1 wt. % to about 20 wt. %, about 3 wt. %to about 8 wt. %, and about 3 wt. % to about 6 wt. %.

Cleaning Fillers

The cleaning composition can include an effective amount of cleaningfillers, which does not perform as a cleaning agent per se, butcooperates with the cleaning agent to enhance the overall cleaningcapacity of the composition. Examples of cleaning fillers suitable foruse in the present cleaning compositions include sodium sulfate, sodiumchloride, starch, sugars, C₁-C₁₀ alkylene glycols such as propyleneglycol, and the like. When the concentrate includes a cleaning filler,it can be included in an amount of between about 1 wt. % and about 20wt. % and between about 3 wt. % and about 15 wt. %.

Stabilizing Agents

Stabilizing agents that can be used in the cleaning composition include,but are not limited to: primary aliphatic amines, betaines, borate,calcium ions, sodium citrate, citric acid, sodium formate, glycerine,malonic acid, organic diacids, polyols, propylene glycol, and mixturesthereof. The concentrate need not include a stabilizing agent, but whenthe concentrate includes a stabilizing agent, it can be included in anamount that provides the desired level of stability of the concentrate.Exemplary ranges of the stabilizing agent include up to about 20 wt. %,between about 0.5 wt. % to about 15 wt. % and between about 2 wt. % toabout 10 wt. %.

Dispersants

Dispersants that can be used in the cleaning composition include maleicacid/olefin copolymers, polyacrylic acid, and its copolymers, andmixtures thereof. The concentrate need not include a dispersant, butwhen a dispersant is included it can be included in an amount thatprovides the desired dispersant properties. Exemplary ranges of thedispersant in the concentrate can be up to about 20 wt. %, between about0.5 wt. % and about 15 wt. %, and between about 2 wt. % and about 9 wt.%.

Hydrotrope

The compositions may optionally include a hydrotrope that aides incompositional stability and aqueous formulation. Functionally speaking,the suitable hydrotrope couplers which can be employed are non-toxic andretain the active ingredients in aqueous solution throughout thetemperature range and concentration to which a concentrate or any usesolution is exposed.

Any hydrotrope coupler may be used provided it does not react with theother components of the composition or negatively affect the performanceproperties of the composition. Representative classes of hydrotropiccoupling agents or solubilizers which can be employed include anionicsurfactants such as alkyl sulfates and alkane sulfonates, linear alkylbenzene or naphthalene sulfonates, secondary alkane sulfonates, alkylether sulfates or sulfonates, alkyl phosphates or phosphonates, dialkylsulfosuccinic acid esters, sugar esters (e.g., sorbitan esters), amineoxides (mono-, di-, or tri-alkyl) and C₈-C₁₀ alkyl glucosides. Preferredcoupling agents include n-octanesulfonate, available as NAS 8D fromEcolab Inc., n-octyl dimethylamine oxide, and the commonly availablearomatic sulfonates such as the alkyl benzene sulfonates (e.g. xylenesulfonates) or naphthalene sulfonates, aryl or alkaryl phosphate estersor their alkoxylated analogues having 1 to about 40 ethylene, propyleneor butylene oxide units or mixtures thereof. Other preferred hydrotropesinclude nonionic surfactants of C₆-C₂₄ alcohol alkoxylates (alkoxylatemeans ethoxylates, propoxylates, butoxylates, and co-or-terpolymermixtures thereof) (preferably C₆-C₁₄ alcohol alkoxylates) having 1 toabout 15 alkylene oxide groups (preferably about 4 to about 10 alkyleneoxide groups); C₆-C₂₄ alkylphenol alkoxylates (preferably C₈-C₁₀alkylphenol alkoxylates) having 1 to about 15 alkylene oxide groups(preferably about 4 to about 10 alkylene oxide groups); C₆-C₂₄alkylpolyglycosides (preferably C₆-C₂₀ alkylpolyglycosides) having 1 toabout 15 glycoside groups (preferably about 4 to about 10 glycosidegroups); C₆-C₂₄ fatty acid ester ethoxylates, propoxylates orglycerides; and C₄-C₁₂ mono or dialkanolamides. A preferred hydrotropeis sodium cumenesulfonate (SCS).

The composition of an optional hydrotrope can be present in the range offrom about 0 to about 25 percent by weight.

Water Conditioning Agent/Chelant

Water conditioning agents function to inactivate water hardness andprevent calcium and magnesium ions from interacting with soils,surfactants, carbonate and hydroxide. Water conditioning agentstherefore improve detergency and prevent long term effects such asinsoluble soil redepositions, mineral scales and mixtures thereof. Waterconditioning can be achieved by different mechanisms includingsequestration, precipitation, ion-exchange and dispersion (thresholdeffect).

The water conditioning agents which can be used include inorganic watersoluble water conditioning agents, inorganic water insoluble waterconditioning agents, organic water soluble conditioning agents, andorganic water insoluble water conditioning agents. Exemplary inorganicwater soluble water conditioning agents include all physical forms ofalkali metal, ammonium and substituted ammonium salts of carbonate,bicarbonate and sesquicarbonate; pyrophosphates, and condensedpolyphosphates such as tripolyphosphate, trimetaphosphate and ring openderivatives; and, glassy polymeric metaphosphates of general structureM_(n)+2P_(n)O₃n+1 having a degree of polymerization n of from about 6 toabout 21 in anhydrous or hydrated forms; and, mixtures thereof.Exemplary inorganic water insoluble water conditioning agents includealuminosilicate builders. Exemplary water soluble water conditioningagents include iminoacetates, polyphosphonates, aminopolyphosphonates,short chain carboxylates and polycarboxylates. Organic water solublewater conditioning agents useful in the compositions of the presentcompositions include aminpolyacetates, polyphosphonates,aminopolyphosphonates, short chain carboxylates and a wide variety ofpolycarboxylate compounds.

Aminopolyacetate water conditioning salts suitable for use hereininclude the sodium, potassium lithium, ammonium, and substitutedammonium salts of the following acids: ethylenediaminetetraacetic acid,N-(2-hydroxyethyl)-ethylenediamine triacetic acid,N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaaceticacid, 1,2-diaminocyclohexanetetracetic acid and nitrilotriacetic acid;and, mixtures thereof. Polyphosphonates useful herein specificallyinclude the sodium, lithium and potassium salts of ethylene diphosphonicacid; sodium, lithium and potassium salts ofethane-1-hydroxy-1,1-diphosphonic acid and sodium lithium, potassium,ammonium and substituted ammonium salts ofethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid,carbonyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid,ethane-2-hydroxy-1,1,2-triphosphonic acid,propane-1,1,3,3-tetraphosphonic acid propane-1,1,2,3-tetraphophonic acidand propane 1,2,2,3-tetraphosphonic acid; and mixtures thereof. Examplesof these polyphosphonic compounds are disclosed in British Pat. No.1,026,366. For more examples see U.S. Pat. No. 3,213,030 to Diehl issuedOct. 19, 1965 and U.S. Pat. No. 2,599,807 to Bersworth issued Jun. 10,1952. Aminopolyphosphonate compounds are excellent water conditioningagents and may be advantageously used. Suitable examples include solublesalts, e.g. sodium, lithium or potassium salts, of diethylene thiaminepentamethylene phosphonic acid, ethylene diamine tetramethylenephosphonic acid, hexamethylenediamine tetramethylene phosphonic acid,and nitrilotrimethylene phosphonic acid; and, mixtures thereof. Watersoluble short chain carboxylic acid salts constitute another class ofwater conditioner for use herein. Examples include citric acid, gluconicacid and phytic acid. Preferred salts are prepared from alkali metalions such as sodium, potassium, lithium and from ammonium andsubstituted ammonium. Suitable water soluble polycarboxylate waterconditioners include the various ether polycarboxylates, polyacetal,polycarboxylates, epoxy polycarboxylates, and aliphatic-, cycloalkane-and aromatic polycarboxylates.

Enzymes

Enzymes can be used to catalyze and facilitate organic and inorganicreactions. It is well known, for example, that enzymes are used inmetabolic reactions occurring in animal and plant life.

The enzymes that can be used include simple proteins or conjugatedproteins produced by living organisms and functioning as biochemicalcatalysts which, in cleaning technology, degrade or alter one or moretypes of soil residues encountered on food process equipment surfacesthus removing the soil or making the soil more removable by the cleaningsystem. Both degradation and alteration of soil residues improvedetergency by reducing the physicochemical forces which bind the soil tothe surface being cleaned, i.e. the soil becomes more water soluble. Theenzyme may be functional in either the acidic, neutral or alkaline pHrange.

Enzymes are extremely effective catalysts. In practice, very smallamounts will accelerate the rate of soil degradation and soil alterationreactions without themselves being consumed in the process. Enzymes alsohave substrate (soil) specificity which determines the breadth of itscatalytic effect. Some enzymes interact with only one specific substratemolecule (absolute specificity); whereas, other enzymes have broadspecificity and catalyze reactions on a family of structurally similarmolecules (group specificity).

Enzymes exhibit catalytic activity by virtue of three generalcharacteristics: the formation of a noncovalent complex with thesubstrate, substrate specificity, and catalytic rate. Many compounds maybind to an enzyme, but only certain types will lead to subsequentreaction. The latter are called substrates and satisfy the particularenzyme specificity requirement. Materials that bind but do not thereuponchemically react can affect the enzymatic reaction either in a positiveor negative way. For example, unreacted species called inhibitorsinterrupt enzymatic activity.

Several enzymes may fit into more than one class. A valuable referenceon enzymes is “Industrial Enzymes”, Scott, D., in Kirk-OthmerEncyclopedia of Chemical Technology, 3rd Edition, (editors Grayson, M.and EcKroth, D.) Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980.

Proteases, a sub-class of hydrolases, are further divided into threedistinct subgroups which are grouped by the pH optima (i.e. optimumenzyme activity over a certain pH range). These three subgroups are thealkaline, neutral and acids proteases. These proteases can be derivedfrom vegetable, animal or microorganism origin; but, preferably are ofthe latter origin which includes yeasts, molds and bacteria. Examples ofsuitable commercially available alkaline proteases are Alkalize®,Savinase®, and Esperase®—all of Novo Industri AS, Denmark; Purafect® ofGenencor International; Maxacal®, Maxapem® and Maxatase®—all ofGist-Brocase International NV, Netherlands; Optimase® and Opticlean® ofSolvay Enzymes, USA and so on.

Commercial alkaline proteases are obtainable in liquid or dried form,are sold as raw aqueous solutions or in assorted purified, processed andcompounded forms, and are comprised of about 2% to about 80% by weightactive enzyme generally in combination with stabilizers, buffers,cofactors, impurities and inert vehicles. The actual active enzymecontent depends upon the method of manufacture and is not critical,assuming the cleaning solution has the desired enzymatic activity. Theparticular enzyme chosen for use in the process and products depend uponthe conditions of final utility, including the physical product form,use pH, use temperature, and soil types to be degraded or altered. Theenzyme can be chosen to provide optimum activity and stability for anygiven set of utility conditions.

Naturally, mixtures of different proteolytic enzymes may be used. Whilevarious specific enzymes have been described above, it is to beunderstood that any protease which can confer the desired proteolyticactivity to the composition may be used.

In addition to proteases, it is also to be understood, and one skilledin the art will see from the above enumeration, that other enzymes whichare well known in the art may also be used with the composition.Included are other hydrolases such as esterases, carboxylases and thelike; and, other enzyme classes.

Further, in order to enhance its stability, the enzyme or enzymeadmixture may be incorporated into various non-liquid embodiments as acoated, encapsulated, agglomerated, prilled or marumerized form. Also,to enhance stability, the enzyme or enzyme admixture may be incorporatedinto various non-aqueous embodiments such as propylene glycol, glycerin,etc.

pH Adjusting Agents

Various pH adjusting agents can be utilized to alter the pH of thetreatment composition. The pH adjusting agents can provide desiredbuffering systems. Exemplary alkaline pH adjusting agents includecarbonate, bicarbonate, sodium hydroxide, tetraborate, and boric acid. Abuffering system that includes carbonate and bicarbonate can provide anexemplary pH of between about 9 and about 10, a buffering system thatincludes carbonate and sodium hydroxide can provide an exemplary pH ofbetween about 9 and about 11, and a buffering system that includessodium tetraborate and boric acid can include a pH of between about 7.6and about 9.2. The pH adjusting agent can include an acid to provide anacidic buffering system. Exemplary acids include citric acid, citrate,acetic acid, acetate, phosphoric acid, and phosphate. For example, abuffering system including citric acid and sodium hydroxide can providean exemplary pH of between about 2.2 and about 6.5, a buffering systemthat includes sodium citrate and citric acid can provide an exemplary pHof between about 3.0 and about 6.2, a buffering system that includessodium acetate and acetic acid can provide an exemplary pH of betweenabout 3.6 and about 5.6, and a buffering system that includes sodiumdihydrogen phosphate and disodium hydrogen phosphate can provide anexemplary pH of between about 5.8 and about 8.0.

Clean in Place

The membrane cleaning compositions and methods are generallyclean-in-place systems (CIP), clean-out-of-place systems (COP), textilelaundry machines, micro, ultra, nano and reverse osmosis filtrationsystems. COP systems can include readily accessible systems includingwash tanks, soaking vessels, mop buckets, holding tanks, scrub sinks,vehicle parts washers, non-continuous batch washers and systems, and thelike. CIP systems include the internal components of tanks, lines, pumpsand other process equipment used for processing typically liquid productstreams such as beverages, milk, and juices. CIP systems are cleanedwithout dismantling the components and without mechanical abrasion suchas scrubbing etc.

Generally, the cleaning of the in-place system or other surface (i.e.,removal of unwanted offal therein) is accomplished with an alkalinecleaning which is introduced with heated water. The compositions may beintroduced during, prior to, or concurrently with the cleaning step (asa separate booster or as part of the cleaning composition) and areapplied or introduced into the system at a use solution concentration inunheated, ambient temperature water. CIP typically employ flow rates onthe order of about 40 to about 600 liters per minute, temperatures fromambient up to about 70° C., and contact times of at least about 10seconds, for example, about 30 to about 120 seconds. The presentcomposition can remain in solution in cold (e.g., 40° F./4° C.) waterand heated (e.g., 140° F./60° C.) water. Although it is not normallynecessary to heat the aqueous use solution of the present composition,under some circumstances heating may be desirable to further enhance itsactivity. These materials are useful at any conceivable temperatures.

Membrane Treating Programs

Various different treatment programs can be used to treat a membrane.The method for treating a membrane can include a plurality of steps. Afirst step can be referred to as a product removal step or displacementwhere product (whey, milk, etc.) is removed from the filtration system.The product can be effectively recovered and used as opposed todischarging as plant effluent. In general, the product removal step canbe characterized as an exchange step where water, gas, or multiple phaseflow displaces the product from the membrane system. The product removalstep can last as long as it takes to remove and recover product from thefiltration system. In general, it is expected that the product removalstep will take at least a couple minutes for most dairy filtrationsystems.

Another step often used can be referred to as a pre-rinse step. Ingeneral, water and/or an alkaline solution can be circulated in thefiltration system to remove gross soils. It should be understood that alarge scale filtration system refers to an industrial system having atleast about 10 membrane vessels, at least about 40 membranes, and atotal membrane area of at least about 200 m². Industrial filtrationsystems for use in dairy and brewery applications often include about 10to about 200 membrane vessels, about 40 to about 1,000 membranes, and atotal membrane area of about 200 m² to about 10,000 m².

Several chemistry treatment cycles can be repeated for acid treatment,alkaline treatment, and neutral treatment. In general, the varioustreatments can be provided with or without an enzyme.

The liquid component can be provided as an alkaline treatment, an acidictreatment, a neutral treatment, a solvent treatment and/or as anenzymatic treatment.

By way of example, the surfactant system can be used in various steps inthe filter cleaning process. For example, rinsing can be accomplishedwith the surfactant system of alone or as a neutral, acidic, or alkalinesolution. Cleaning can be accomplished using a cleaning composition thatcan include alkaline, acid, enzymes, non-aqueous components, and/or thesurfactant system. Sanitizing and/or preserving can be accomplished witha composition that includes chlorine, acids, peracids, and/or reducingcompositions. A penetrant is generally considered to be a component thatpenetrates into the soil and softens the soil for removal. The penetrantcan be selected for the particular type of soil expected on themembrane. In the case of membranes used in the dairy industry, it isexpected that the penetrant will be selected to provide for penetrationinto protein and lipid soils.

Forming a Concentrate

The concentrate composition can be provided as a solid, liquid, or gel,or a combination thereof. In one embodiment, the cleaning compositionsmay be provided as a concentrate such that the cleaning composition issubstantially free of any added water or the concentrate may contain anominal amount of water. The concentrate can be formulated without anywater or can be provided with a relatively small amount of water inorder to reduce the expense of transporting the concentrate. Forexample, the composition concentrate can be provided as a capsule orpellet of compressed powder, a solid, or loose powder, either containedby a water soluble material or not. In the case of providing the capsuleor pellet of the composition in a material, the capsule or pellet can beintroduced into a volume of water, and if present the water solublematerial can solubilize, degrade, or disperse to allow contact of thecomposition concentrate with the water. For the purposes of thisdisclosure, the terms “capsule” and “pellet” are used for exemplarypurposes and are not intended to limit the delivery mode to a particularshape.

When provided as a liquid concentrate composition, the concentrate canbe diluted through dispensing equipment using aspirators, peristalticpumps, gear pumps, mass flow meters, and the like. This liquidconcentrate embodiment can also be delivered in bottles, jars, dosingbottles, bottles with dosing caps, and the like. The liquid concentratecomposition can be filled into a multi-chambered cartridge insert thatis then placed in a spray bottle or other delivery device filled with apre-measured amount of water.

In yet another embodiment, the concentrate composition can be providedin a solid form that resists crumbling or other degradation until placedinto a container. Such container may either be filled with water beforeplacing the composition concentrate into the container, or it may befilled with water after the composition concentrate is placed into thecontainer. In either case, the solid concentrate composition dissolves,solubilizes, or otherwise disintegrates upon contact with water. In aparticular embodiment, the solid concentrate composition dissolvesrapidly thereby allowing the concentrate composition to become a usecomposition and further allowing the end user to apply the usecomposition to a surface in need of cleaning. When the cleaningcomposition is provided as a solid, the compositions provided above maybe altered in a manner to solidify the cleaning composition by any meansknown in the art. For example, the amount of water may be reduced oradditional ingredients may be added to the cleaning composition, such asa solidification agent.

In another embodiment, the solid concentrate composition can be dilutedthrough dispensing equipment whereby water is sprayed at the solid blockforming the use solution. The water flow is delivered at a relativelyconstant rate using mechanical, electrical, or hydraulic controls andthe like. The solid concentrate composition can also be diluted throughdispensing equipment whereby water flows around the solid block,creating a use solution as the solid concentrate dissolves. The solidconcentrate composition can also be diluted through pellet, tablet,powder and paste dispensers, and the like.

The water used to dilute the concentrate (water of dilution) can beavailable at the locale or site of dilution. The water of dilution maycontain varying levels of hardness depending upon the locale. Servicewater available from various municipalities have varying levels ofhardness. It is desirable to provide a concentrate that can handle thehardness levels found in the service water of various municipalities.The water of dilution that is used to dilute the concentrate can becharacterized as hard water when it includes at least 1 grain hardness.It is expected that the water of dilution can include at least 5 grainshardness, at least 10 grains hardness, or at least 20 grains hardness.

It is expected that the concentrate will be diluted with the water ofdilution in order to provide a use solution having a desired level ofdetersive properties. If the use solution is required to remove tough orheavy soils, it is expected that the concentrate can be diluted with thewater of dilution at a weight ratio of at least 1:1 and up to 1:8. If alight duty cleaning use solution is desired, it is expected that theconcentrate can be diluted at a weight ratio of concentrate to water ofdilution of up to about 1:256.

In an alternate embodiment, the cleaning compositions may be provided asa ready-to-use (RTU) composition. If the cleaning composition isprovided as a RTU composition, a more significant amount of water isadded to the cleaning composition as a diluent. When the concentrate isprovided as a liquid, it may be desirable to provide it in a flowableform so that it can be pumped or aspirated. It has been found that it isgenerally difficult to accurately pump a small amount of a liquid. It isgenerally more effective to pump a larger amount of a liquid.Accordingly, although it is desirable to provide the concentrate with aslittle water as possible in order to reduce transportation costs, it isalso desirable to provide a concentrate that can be dispensedaccurately. In the case of a liquid concentrate, it is expected thatwater will be present in an amount of up to about 90 wt. %, particularlybetween about 20 wt. % and about 85 wt. %, more particularly betweenabout 30 wt. % and about 80 wt. % and most particularly between about 50wt. % and about 80 wt. %.

In the case of a RTU composition, it should be noted that theabove-disclosed cleaning composition may, if desired, be further dilutedwith up to about 96 wt. % water, based on the weight of the cleaningcomposition.

The cleaning composition may be made using a mixing process. Thesurfactant booster composition and/or cleaning composition comprisingthe same and other functional ingredients are mixed for an amount oftime sufficient to form a final, homogeneous composition. In anexemplary embodiment, the components of the cleaning composition aremixed for approximately 10 minutes.

A solid cleaning composition as used in the present disclosureencompasses a variety of forms including, for example, solids, pellets,blocks, tablets, and powders. By way of example, pellets can havediameters of between about 1 mm and about 10 mm, tablets can havediameters of between about 1 mm and about 10 mm or between about 1 cmand about 10 cm, and blocks can have diameters of at least about 10 cm.It should be understood that the term “solid” refers to the state of thecleaning composition under the expected conditions of storage and use ofthe solid cleaning composition. In general, it is expected that thecleaning composition will remain a solid when provided at a temperatureof up to about 100° F. or lower than about 120° F.

In certain embodiments, the solid cleaning composition is provided inthe form of a unit dose. A unit dose refers to a solid cleaningcomposition unit sized so that the entire unit is used during a singlecycle. When the solid cleaning composition is provided as a unit dose,it can have a mass of about 1 g to about 50 g. In other embodiments, thecomposition can be a solid, a pellet, or a tablet having a size of about50 g to 250 g, of about 100 g or greater, or about 40 g to about 11,000g.

In other embodiments, the solid cleaning composition is provided in theform of a multiple-use solid, such as, a block or a plurality ofpellets, and can be repeatedly used to generate aqueous cleaningcompositions for multiple washing cycles. In certain embodiments, thesolid cleaning composition is provided as a solid having a mass of about5 g to about 10 kg. In certain embodiments, a multiple-use form of thesolid cleaning composition has a mass of about 1 kg to about 10 kg. Infurther embodiments, a multiple-use form of the solid cleaningcomposition has a mass of about 5 kg to about 8 kg. In otherembodiments, a multiple-use form of the solid cleaning composition has amass of about 5 g to about 1 kg, or about 5 g and to about 500 g.

The components can be mixed and extruded or cast to form a solid such aspellets, powders or blocks. Heat can be applied from an external sourceto facilitate processing of the mixture.

A mixing system provides for continuous mixing of the ingredients athigh shear to form a substantially homogeneous liquid or semi-solidmixture in which the ingredients are distributed throughout its mass.The mixing system includes means for mixing the ingredients to provideshear effective for maintaining the mixture at a flowable consistency,with a viscosity during processing of about 1,000-1,000,000 cP,preferably about 50,000-200,000 cP. The mixing system can be acontinuous flow mixer or a single or twin screw extruder apparatus.

The mixture can be processed at a temperature to maintain the physicaland chemical stability of the ingredients, such as at ambienttemperatures of about 20-80° C., and about 25-55° C. Although limitedexternal heat may be applied to the mixture, the temperature achieved bythe mixture may become elevated during processing due to friction,variances in ambient conditions, and/or by an exothermic reactionbetween ingredients. Optionally, the temperature of the mixture may beincreased, for example, at the inlets or outlets of the mixing system.

An ingredient may be in the form of a liquid or a solid such as a dryparticulate, and may be added to the mixture separately or as part of apremix with another ingredient, as for example, the scale controlcomponent may be separate from the remainder of the cleaningcomposition. One or more premixes may be added to the mixture.

The ingredients are mixed to form a substantially homogeneousconsistency wherein the ingredients are distributed substantially evenlythroughout the mass. The mixture can be discharged from the mixingsystem through a die or other shaping means. The profiled extrudate canbe divided into useful sizes with a controlled mass. The extruded solidcan be packaged in film. The temperature of the mixture when dischargedfrom the mixing system can be sufficiently low to enable the mixture tobe cast or extruded directly into a packaging system without firstcooling the mixture. The time between extrusion discharge and packagingcan be adjusted to allow the hardening of the cleaning block for betterhandling during further processing and packaging. The mixture at thepoint of discharge can be about 20-90° C., and about 25-55° C. Thecomposition can be allowed to harden to a solid form that may range froma low density, sponge-like, malleable, caulky consistency to a highdensity, fused solid, concrete-like block.

Optionally, heating and cooling devices may be mounted adjacent tomixing apparatus to apply or remove heat in order to obtain a desiredtemperature profile in the mixer. For example, an external source ofheat may be applied to one or more barrel sections of the mixer, such asthe ingredient inlet section, the final outlet section, and the like, toincrease fluidity of the mixture during processing. Preferably, thetemperature of the mixture during processing, including at the dischargeport, is maintained preferably at about 20-90° C.

When processing of the ingredients is completed, the mixture may bedischarged from the mixer through a discharge die. The solidificationprocess may last from a few minutes to about six hours, depending, forexample, on the size of the cast or extruded composition, theingredients of the composition, the temperature of the composition, andother like factors. Preferably, the cast or extruded composition “setsup” or begins to harden to a solid form within about 1 minute to about 3hours, preferably about 1 minute to about 2 hours, most preferably about1 minute to about 1.0 hours minutes.

The concentrate can be provided in the form of a liquid. Various liquidforms include gels and pastes. Of course, when the concentrate isprovided in the form of a liquid, it is not necessary to harden thecomposition to form a solid. In fact, it is expected that the amount ofwater in the composition will be sufficient to preclude solidification.In addition, dispersants and other components can be incorporated intothe concentrate in order to maintain a desired distribution ofcomponents.

In certain embodiments, the cleaning composition may be mixed with awater source prior to or at the point of use. In other embodiments, thecleaning compositions do not require the formation of a use solutionand/or further dilution and may be used without further dilution.

In aspects employing solid cleaning compositions, a water sourcecontacts the cleaning composition to convert solid cleaningcompositions, particularly powders, into use solutions. Additionaldispensing systems may also be utilized which are more suited forconverting alternative solid cleanings compositions into use solutions.The methods of the include use of a variety of solid cleaningcompositions, including, for example, extruded blocks or “capsule” typesof package.

In an aspect, a dispenser may be employed to spray water (e.g. in aspray pattern from a nozzle) to form a cleaning use solution. Forexample, water may be sprayed toward an apparatus or other holdingreservoir with the cleaning composition, wherein the water reacts withthe solid cleaning composition to form the use solution. In certainembodiments of the methods, a use solution may be configured to dripdownwardly due to gravity until the dissolved solution of the cleaningcomposition is dispensed for use.

EXAMPLES Example 1

Cloud Point Study

The cloud point is the temperature in which a surfactant is no longermiscible in water and thus precipitates out of the solution as oil. Asurfactant above its cloud point will not clean as well as one below itscloud point, but a surfactant above its cloud point will defoam betterthan a surfactant below its cloud point. Basically, cloud point can bevisually detected when the solution becomes turbid as temperatureincreases. In this work, we applied the turbidity meter for a cloudpoint detection.

For our measurement, a 1000 mL of aqueous surfactant solution wasprepared at 1% w/v at pH 11. The temperature was increased at a constantrate with proper agitation to ensure a uniform solution temperaturewhile not creating the bubble from too strong agitation. Turbidityreadings were taken automatically and the slope of the turbidity vs timecan be calculated. The cloud point was taken at the point where thesharp change of slope occurred.

As temperature closes to cloud point, the nonionic surfactant becomesmore hydrophobic. Once the temperature is above the cloud point, thenonionic surfactant becomes oil-like phase, loses its detergency, andfouls the membrane, as shown in Tables A and B.

Ecosurf EH-3 is a branched (2-ethyl-hexyl alkoxylate) C8 ethyl hexyl(PO)₅(EO)₃ nonionic extended surfactant commercially available from DowChemical, Midland Mich.

Ecosurf EH-6 is a is a commercially available branched C8 ethyl hexyl(PO)₅(EO)₆ nonionic extended surfactant

Ecosurf EH-9 is a is a commercially available branched C8 ethyl hexyl(PO)₅(EO)₉ nonionic extended surfactant

Results are shown in Table A and B

TABLE A Result of coupon test Temperature 50 C., pH 11, 10 min, actives= 1000 ppm % butterfat removal from PS coupon Cmc (RT, @50 C. Cloudpoint w/o salt) Ecosurf EH-3 47.8 * 480 Ecosurf EH-6 72.1 40 914 EcosurfEH-9 84.6 64 1066

TABLE B % butterfat removal from * Experimental PS coupon XL @40 C.Cloud point Cmc 3PH-8PO3EO 29.5 2.97 2397 3PH-8PO6EO 53.1 19.7 11903PH-8PO8EO 54.9 32.51 485 3PH-8EO10EO 62.9 46.95 185 Experimental XL ispropyl heptyl (PO)m (EO)n Temperature 40 C., pH 11, 10 min, actives =1000 ppm

Example 2

Mechanistic Study of Butterfat Removal—Dynamic Interfacial Tension(IFT_(dyn)) Measurement

Dynamic interfacial tension measurements were performed using a spinningdrop Tensiometer (SVT15N). A small volume of liquid ghee was injectedinto a capillary containing the aqueous surfactant solution at pH 11.The capillary was spun at 4000 rpm in a constant controlled chamber attemperature of 50 C. The IFT_(dyn) value was taken once the interfacialtension reached the equilibrium or at 30 min.

Dynamic IFT was measured at 50° C., 4000 rpm against peanut oil, palmoil, and ghee. Results are shown in FIGS. 1, 2, and 3, respectively.From the figures one can see that Commercially available membranecleaning product with NPE, Commercially available cleaning product withcocoamine oxide, and EH9 have comparable low interfacial tension againstpeanut oil, palm oil and ghee (less than 7).

Example 3

Wettability of Cleaning Solution on Polysulfone (PS) Coupon by ContactAngle Measurement.

The lower contact angle means the solution can wet the surface well.FIGS. 4 and 5 show the contact angle measurement of Commerciallyavailable membrane cleaning product with NPE, Commercially availablecleaning product with cocoamine oxide and EH 9. The results show that EH9 and NPE containing commercial composition can wet PS coupon muchfaster than cocaine oxide composition and water. EH9 and the NPEcompositions are best at removing butterfat from the PS coupon.

Example 4

Blend Testing

Different surfactants were tested in combination with the EH extendedsurfactants to see if any synergies were present.

Lutensol TO5 is a saturated iso-C13alcohol available from BASF

Surfynol is a nonionic polyoxyethylene substituted acetylene glycolsurfactant commercially available from Evonik Industries

Dynol 604 and Dynal 360 are Gemini surfactants available from AirProducts.

Stability data was also tested and is listed in Table C below.

TABLE C separated Freeze thaw Blend (RT, 7 days) (4 cycles) EH9/TO590/10 Y Y EH9/TO5 70/30 Y Y EH9/TO5 50/50 Y Y EH9 N N TO5 N N EH9/Surf440 90/10 Y Y EH9/Surf 440 60/40 N Y EH9/Dyn 604 90/10 Y Y EH9/Dyn 60460/40 N Y EH9/Dyn 360 90/10 N Y EH9/Dyn 360 60/40 Y Y

-   -   Although a few blends were stable at room temp after 7 days,        none were stable after 4 freeze thaw cycles

Initial raw material comparisons were done to see how the other 3surfactants behave in comparison to EH9 for contact angle. The resultsare shown in FIGS. 5-9. From the graphs, we can see that EH9/XP40 blendshad shown the most promise in wettability. The blends were tested formstability date and the results are shown in Table C.

Next IFT was measured for Ecosurf EH9, Lutensol XP40 (Guerbet alcoholethoxylate) Pluronic (inverse EO/PO block copolymer 25R2, and EH9/XP40blend to compare how they may emulsify butterfat. From FIG. 10 we cansee that the EH9/XP40 blend will be a better cleaning surfactant due toits superior wetting ability and lower interfacial tension with ghee.

Next butterfat removal was tested. The butterfat removal data in FIG. 11shows that there is no statistical difference between the cleaningability of EH9 and any of the surfactant blends with XP40.

From the data, so far one can see that the removal of butterfat from themembrane is a combination of wettability, emulsification, and cloudpoint for nonionic ethoxylate surfactants. Although no statisticaldifference between EH9 and XP40 cleaning can be seen in the currentdata, it has been observed that XP40 does not remove butterfat soil aseffectively as EH9 at the conditions of 1000 ppm, pH11, and 50 C. Thisprovides evidence that cleaning below the cloud point is critical inbutterfat removal.

Example 5

In general practice, the cleaning of membrane for dairy plants by asurfactant solution is carried out at cleaning temperature of 50° C. andpH of 11. The data has shown that the combination of a cloud point ofnonionic surfactant solution slightly above the cleaning temperature, alow interfacial tension against butter fat, and a low contact againstmembrane materials are needed to achieve overall fat soil removal on themembrane. The combination of these traits allows the surfactant to bemost effective at cleaning butterfat soils from membrane systems.

The contact angle was measured on polysulfone coupon at room temperatureas the surfactants used in our study could reach the cloud point andseparate out from the solution. Polysulfone was chosen as it is usedmostly as a material for membrane in dairy plants. A low contact anglemeans the surfactant will spread more easily on the membrane and help tolift the butter soil off of the membrane, high contact angles mean thesurfactant is not able to effectively spread on the membrane and comesin less contact with the butterfat soils.

The nonionic surfactant system used in our cleaning formula exhibitscloud point phenomena where it will remain surface active and misciblein aqueous solution at the temperature below the cloud point. At atemperature above the cloud point, the nonionic surfactant in thecleaning solution separates out as a coacervate phase or oil phase andloses its surface active properties. The oily phase combining with theoily soil can lead to higher soil loads and become more difficult toremove as they have strong attachment on the membrane which is mostlyhydrophobic. A low interfacial tension (IFT) value with butterfat meansthe surfactant is able to effectively emulsify butterfat, reducingredepositing on the membrane system.

In comparing surfactants, it was found that Ecosurf EH9 possessed all ofthe favorable butterfat removal traits. It had a low contact angle onpolysulfone, a cloud point above 50° C., and a low IFT against ghee orclarified butter fat. In comparing against other surfactants it wasfound that no others possessed all 3 favorable traits. Ecosurf EH6 has acomparable contact angle to EH9, a cloud point close to but still lowerthan 50° C., and a higher IFT value than EH9. Thus, it was expected itwould have a lower percentage of butterfat removal, which is what wasfound. Ecosurf EH-3, with an even lower cloud point, was also shown tobe worse than EH6, also giving rise to the importance of cloud pointwith butterfat removal. Surfonic X-AES has no cloud point as it is ananionic surfactant and a lower IFT value than EH9, leading one tobelieve it may outperform on butterfat removal in comparison to EH9 butit has a much higher contact angle on polysulfone. With a high contactangle on the membrane, the surfactant may not be able to adequatelyreach enough of the butterfat soil to effectively remove it from themembrane.

See Table D.

TABLE D Butterfat removal percentage next to the cloud point of eachsurfactant, run at 1000 ppm, pH 11 Chemistry Butterfat removal (%) cloudpoint (C. °)* EH9 88.6 49.00 EH3 43.50 12.67 EH6 52.5 40.00 SLF-18026.65 23.22 Pluronic 25R4 57.14 41.42 Surfonic X-AES 20.32 none DehyponLS-36 19.37 12.00 Plurafac LF500 32.05 32 (5 g of surfactant in 25 g ofdiethylene glycol monobutyl ether solution (C = 250 g/L)) *1 g ofsurfactant in 100 g of DI water.

Example 6

Butterfat Removal Tests

Pluronic 25R2: Polyoxypropylene polyoxyethylene block (reverse)

Plurifac LF-500: alcohol ethoxylate propoxylate

Dehypon E127: Fatty alcohol alkoxylate

SLf-18B45: alcohol alkoxylate

Novel II 1012-GB-21: alcohol ethoxylate C10-12, 21EO

Butterfat removal tests were run on numerous different surfactants onpolysulfone Coupons. Each coupon was washed with a 0.50 wt % soapsolution (using a saturated towel), then DI rinse and patted dry. Thecoupons were then dipped twice in Methanol and allowed to air dry overnight before weighing on an analytical balance. Soil used was unsaltedbutter/approx. weights of 0.020-0.025 grams (applied to coupon using 1″foam paint brush). The beaker size=1000 ml, volume of test soln=600 ml,product test solution concentration=0.05 wt %, test soln temperature was120° F. The test solution pH was 11.00 (the DI water or solutionscontaining test product are adjusted to pH 11.00 after the solutionreaches 120 F, prior to submerging coupons), the stir bar size was 5 CM,stirring speed during test=250 RPM with 10 min exposure time. Theresults are below in Table E.

TABLE E post cleaning coupon/ coupon/ coupon/soil Clean soil soil soilwt wt (g) weight % soil coupon coupon wt (g) wt (g) (g) after dryingsoil (g) % soil % soil removed Product # wt. initial wt. next day nextday overnight remains remains removed average Product U-01 1 3.78323.8078 3.8055 0.0223 3.7828 −0.0004 −1.79 101.8 U-01 U-01 2 3.91203.9358 3.9328 0.0208 3.9105 −0.0015 −7.21 107.2 U-01 U-01 3 3.85743.8830 3.8798 0.0224 3.8560 −0.0014 −6.25 106.3 105.1 U-01 DI H2O 43.9509 3.9784 3.9748 0.0239 3.9671 0.0162 67.78 32.2 DI H2O pH 11.00 DIH2O 5 3.9442 3.9681 3.9657 0.0215 3.9543 0.0101 46.98 53.0 DI H2O pH11.00 DI H2O 6 3.8135 3.8388 3.8366 0.0231 3.8239 0.0104 45.02 55.0 46.7DI H2O pH 11.00 U-07 7 3.9902 4.0150 4.0121 0.0219 3.9986 0.0084 38.3661.6 U-07 U-07 8 3.8005 3.8282 3.8247 0.0242 3.8141 0.0136 56.20 43.8U-07 U-07 9 3.8715 3.8982 3.8962 0.0247 3.8820 0.0105 42.51 57.5 54.3U-07 U-06 10 3.9624 3.9870 3.9831 0.0207 3.9718 0.0094 45.41 54.6 U-06U-06 11 3.9124 3.9393 3.9356 0.0232 3.9263 0.0139 59.91 40.1 U-06 U-0612 3.9390 3.9634 3.9605 0.0215 3.9476 0.0086 40.00 60.0 51.6 U-06Butter-Fat Removal Test 2

For this test the polysulfone coupons were conditioned by soaking inMethyl alcohol for 30 seconds, then placed in the 122° F. oven for 30min. Soil was unsalted butter/approx. weights of 0.025-0.030 grams(applied to coupon using 1″ foam paint brush) stir bar size=3.75 CM,stirring speed during test=240 RPM. Results are in Table F

TABLE F post cleaning 10 min coupon/ Coupon/soil exposure time Cleansoil soil wt wt (g) weight % coupon Solution coupon wt (g) (g) afterdrying soil (g) % soil % soil removed # Product % Conc. wt. (g) next daynext day overnight remains remains removed average 1 DI H2O n/a 4.00904.0356 0.0266 4.0310 0.022 82.71 17.3 pH 11.00 2 DI H2O n/a 3.72193.7527 0.0308 3.7451 0.0232 75.32 24.7 pH 11.00 3 DI H2O n/a 4.07784.1042 0.0264 4.0997 0.0219 82.95 17.0 19.7 pH 11.00 4 Commercial 0.05%4.0516 4.0794 0.0278 4.0568 0.0052 18.71 81.3 Product A (with NPE) 5Commercial 0.05% 3.9602 3.9871 0.0269 3.9645 0.0043 15.99 84.0 Product A(with NPE) 6 Commercial 0.05% 3.9567 3.9843 0.0276 3.9615 0.0048 17.3982.6 82.6 Product A (with NPE) 7 Commercial 0.05% 3.8789 3.9059 0.02703.9015 0.0226 83.70 16.3 Product B (no NPE) 8 Commercial 0.05% 3.95793.9822 0.0243 3.9742 0.0163 67.08 32.9 Product B (no NPE) 9 Commercial0.05% 3.7978 3.8259 0.0281 3.8204 0.0226 80.43 19.6 22.9 Product B (noNPE) 10 Commercial 0.05%/0.05% 4.0210 4.0511 0.0301 4.0434 0.0224 74.4225.6 Product B (no NPE)/ Ultrasil 84 11 Commercial 0.05%/0.05% 3.83333.8595 0.0262 3.8550 0.0217 82.82 17.2 Product B (no NPE)/ Ultrasil 8412 Commercial 0.05%/0.05% 3.8096 3.8381 0.0285 3.8302 0.0206 72.28 27.723.5 Product B (no NPE)/ Ultrasil 84 13 Tornado 1 0.05%/0.05% 3.69703.7236 0.0266 3.7187 0.0217 81.58 18.4 25-7/25-3 14 Tornado 10.05%/0.05% 3.8275 3.8568 0.0293 3.8416 0.0141 48.12 51.9 25-7/25-3 15Tornado 1 0.05%/0.05% 3.9245 3.9487 0.0242 3.9436 0.0191 78.93 21.1 30.525-7/25-3 16 LAS/ 0.10% 3.9437 3.9716 0.0279 3.9646 0.0209 74.91 25.1RM171074 17 LAS/ 0.10% 3.9620 3.9941 0.0321 3.9853 0.0233 72.59 27.4RM171074 18 LAS/ 0.10% 3.7867 3.8157 0.0290 3.8084 0.0217 74.83 25.225.9 RM171074 19 *LAS/+50 0.10% 3.8332 3.8633 0.0301 3.8540 0.0208 69.1030.9 ppm Mg 20 *LAS/+50 0.10% 4.0841 4.1134 0.0293 4.1059 0.0218 74.4025.6 ppm Mg 21 *LAS/+50 0.10% 3.7411 3.7682 0.0271 3.7611 0.02 73.8026.2 27.6 ppm Mg 22 **LAS/+100 0.10% 3.7436 3.7652 0.0216 3.7608 0.017279.63 20.4 ppm Mg 23 **LAS/+100 0.10% 3.8401 3.8665 0.0264 3.8599 0.019875.00 25.0 ppm Mg 24 **LAS/+100 0.10% 3.7709 3.8017 0.0308 3.7950 0.024178.25 21.8 22.4 ppm Mg *LAS/+50 ppm Mg added 0.1175 grams MgCl2 added0.1175 grams MgCl2 × .2552 (Mg is 25.52% of MgCl2 compound)/ 600 gramsvolume × 100 × 10000 = 49.97 ppm Mg **LAS/+100 ppm Mg added 0.2350 gramsMgCl2 × .2552 (Mg is 25.52% of MgCl2 compound)/ 600 grams volume × 100 ×10000 = 99.95 ppm Mg Tomadol 91-6: a C₉-C₁₁ alcohol ethoxylate with 6moles EO having a cloud point of between about 47 and about 58° C.,available from Air Products, located in Allentown, PAButterfat removal Test 3 (same conditions as test 2. Table G.)

TABLE G post cleaning 10 min coupon/ coupon/soil exposure time Cleansoil soil wt wt (g) weight % coupon Solution coupon wt (g) (g) afterdrying soil (g) % soil % soil removed # Product % Conc. wt. (g) next daynext day overnight remains remains removed average 1 DI H2O n/a 3.61803.6432 0.0252 3.6363 0.0183 72.62 27.4 pH 11.00 2 DI H2O n/a 3.53393.5603 0.0264 3.5512 0.0173 65.53 34.5 pH 11.00 3 DI H2O n/a 3.62133.6443 0.0230 3.6369 0.0156 67.83 32.2 31.3 pH 11.00 4 Commercial 0.05%3.5696 3.5956 0.0260 3.5716 0.002 7.69 92.3 Product A (with NPE) 5Commercial 0.05% 3.6599 3.6869 0.0270 3.6614 0.0015 5.56 94.4 Product A(with NPE) 6 Commercial 0.05% 3.4872 3.5111 0.0239 3.4903 0.0031 12.9787.0 91.3 Product A (with NPE) 7 LAS/RM171074 0.15% 3.5257 3.5532 0.02753.5444 0.0187 68.00 32.0 8 LAS/RM171074 0.15% 3.0983 3.1252 0.02693.1129 0.0146 54.28 45.7 9 LAS/RM171074 0.15% 3.4814 3.5093 0.02793.4988 0.0174 62.37 37.6 38.5 10 *LAS/+50 0.15% 3.5876 3.6132 0.02563.6026 0.015 58.59 41.4 ppm Mg 11 *LAS/+50 0.15% 3.7151 3.7418 0.02673.7310 0.0159 59.55 40.4 ppm Mg 12 *LAS/+50 0.15% 3.4792 3.5022 0.02303.4951 0.0159 69.13 30.9 37.6 ppm Mg 13 **LAS/+100 0.15% 3.5114 3.53860.0272 3.5276 0.0162 59.56 40.4 ppm Mg 14 **LAS/+100 0.15% 3.4931 3.52070.0276 3.5107 0.0176 63.77 36.2 ppm Mg 15 **LAS/+100 0.15% 3.6589 3.68490.0260 3.6787 0.0198 76.15 23.8 33.5 ppm Mg 16 Tomadol 1-5 0.10% 3.71683.7443 0.0275 3.7340 0.0172 62.55 37.5 17 Tomadol 1-5 0.10% 3.47093.4973 0.0264 3.4841 0.0132 50.00 50.0 18 Tomadol 1-5 0.10% 3.72833.7573 0.0290 3.7451 0.0168 57.93 42.1 43.2 19 Tomadol 900 0.10% 3.58923.6181 0.0289 3.6028 0.0136 47.06 52.9 20 Tomadol 900 0.10% 3.58433.6142 0.0299 3.6031 0.0188 62.88 37.1 21 Tomadol 900 0.10% 3.49883.5257 0.0269 3.5146 0.0158 58.74 41.3 43.8 22 Tomadol 0.05/0.05% 3.54293.5700 0.0271 3.5547 0.0118 43.54 56.5 1-9/1-5 23 Tomadol 0.05/0.05%3.6919 3.7180 0.0261 3.7024 0.0105 40.23 59.8 1-9/1-5 24 Tomadol0.05/0.05% 3.6394 3.6672 0.0278 3.6503 0.0109 39.21 60.8 59.0 1-9/1-5Test 4

TABLE H post cleaning 10 min coupon/ coupon/soil exposure Clean soilsoil wt wt (g) weight % coupon time Solution coupon wt (g) (g) afterdrying soil (g) % soil % soil removed # Product % Conc. wt. (g) next daynext day overnight remains remains removed average 1 Lutensol 0.10%3.5063 3.5332 0.0269 3.5321 0.0258 95.91 4.1 XP-40 2 Lutensol 0.10%3.5696 3.5957 0.0261 3.5887 0.0191 73.18 26.8 XP-40 3 Lutensol 0.10%3.5473 3.5779 0.0306 3.5608 0.0135 44.12 55.9 28.9 XP-40 4 Lutensol0.10% 3.5451 3.5752 0.0301 3.5557 0.0106 35.22 64.8 XP-50 5 Lutensol0.10% 3.5715 3.5985 0.0270 3.5886 0.0171 63.33 36.7 XP-50 6 Lutensol0.10% 3.739 3.7669 0.0279 3.7548 0.0158 56.63 43.4 48.3 XP-50 7 Lutensol0.10% 3.5798 3.607 0.0272 3.5893 0.0095 34.93 65.1 XP-80 8 Lutensol0.10% 3.4553 3.4839 0.0286 3.4664 0.0111 38.81 61.2 XP-80 9 Lutensol0.10% 3.589 3.6162 0.0272 3.5999 0.0109 40.07 59.9 62.1 XP-80 10Ultrasil 06 0.50% 3.4660 3.4947 0.0287 3.469 0.003 10.45 89.5 11Ultrasil 06 0.50% 3.166 3.1952 0.0292 3.1704 0.0044 15.07 84.9 12Ultrasil 06 0.50% 3.4731 3.5011 0.0280 3.4802 0.0071 25.36 74.6 83.0 13Ultrasil 07 0.23% 3.1993 3.2222 0.0229 3.2095 0.0102 44.54 55.5 14Ultrasil 07 0.23% 3.7403 3.7676 0.0273 3.7538 0.0135 49.45 50.5 15Ultrasil 07 0.23% 3.7703 3.799 0.0287 3.7777 0.0074 25.78 74.2 60.1 16Dehypon 0.10% 3.6678 3.6943 0.0265 3.6913 0.0235 88.68 11.3 LS-54 17Dehypon 0.10% 3.5606 3.5896 0.0290 3.5853 0.0247 85.17 14.8 LS-54 18Dehypon 0.10% 3.5421 3.5693 0.0272 3.5644 0.0223 81.99 18.0 14.7 LS-5419 Commercial 0.05% 3.4853 3.5115 0.0262 3.4864 0.0011 4.20 95.8 PRoductA (with NPE) 20 Commercial 0.05% 3.7445 3.7714 0.0269 3.7446 0.0001 0.3799.6 PRoduct A (with NPE) 21 Commercial 0.05% 3.6157 3.6441 0.0284 3.6170.0013 4.58 95.4 97.0 PRoduct A (with NPE) 22 DI water n/a 3.1461 3.17230.0262 3.1624 0.0163 62.21 37.8 pH 11.00 23 DI water n/a 3.5516 3.57780.0262 3.5665 0.0149 56.87 43.1 pH 11.00 24 DI water n/a 3.6628 3.69040.0276 3.6818 0.019 68.84 31.2 37.4 pH 11.00 post cleaning coupon/coupon/soil Clean soil wt weight % coupon Solution coupon wt soil wtafter drying soil % soil % soil removed # Product % Conc. wt. next daynext day overnight remains remains removed average 25 Ethyl Hexyl 0.25%3.5066 3.5333 0.0267 3.5214 0.0148 55.43 44.6 Sulfate 40% 26 Ethyl Hexyl0.25% 3.5434 3.5703 0.0269 3.5593 0.0159 59.11 40.9 Sulfate 40% 27 EthylHexyl 0.25% 3.1386 3.1653 0.0267 3.1524 0.0138 51.69 48.3 44.6 Sulfate40% 28 Tomadol .05%/.05% 3.6716 3.6985 0.0269 3.6824 0.0108 40.15 59.91-9/1-3 29 Tomadol .05%/.05% 3.6149 3.6428 0.0279 3.629 0.0141 50.5449.5 1-9/1-3 30 Tomadol .05%/.05% 3.6709 3.6977 0.0268 3.6865 0.015658.21 41.8 50.4 1-9/1-3 31 Pluafac 0.10% 3.1367 3.1637 0.0270 3.15890.0222 82.22 17.8 LF-900 32 Pluafac 0.10% 3.6801 3.7071 0.0270 3.70280.0227 84.07 15.9 LF-900 33 Pluafac 0.10% 3.5249 3.5506 0.0257 3.54590.021 81.71 18.3 17.3 LF-900 34 Tomadol .075%/.025% 3.6182 3.6468 0.02863.6286 0.0104 36.36 63.6 25-7/25-3 35 Tomadol .075%/.025% 3.523 3.55110.0281 3.5412 0.0182 64.77 35.2 25-7/25-3 36 Tomadol .075%/.025% 3.45833.4841 0.0258 3.4738 0.0155 60.08 39.9 46.3 25-7/25-3Examples of suitable nonionic surfactants include alkoxylatedsurfactants, such as Dehypon LS-54 (R-(EO)₅(PO)₄) and Dehypon LS-36(R-(EO)₃(PO)₆); and capped alcohol alkoxylates, such as Plurafac LF221and Genepol from Clariant, Tegoten EC11; mixtures thereof, or thelike.))Butter-Fat Removal Test 5

TABLE I post cleaning 10 min coupon/ coupon/soil exposure Clean soilsoil wt wt (g) weight % coupon time Solution coupon wt (g) (g) afterdrying soil % soil % soil removed # Product % Conc. wt. (g) next daynext day overnight remains remains removed average 1 DI water n/a 3.90533.9325 0.0272 3.9219 0.0166 61.03 39.0 pH 11.00 2 DI water n/a 3.87963.9074 0.0278 3.8977 0.0181 65.11 34.9 pH 11.00 3 DI water n/a 3.80713.8351 0.0280 3.8245 0.0174 62.14 37.9 37.2 pH 11.00 4 Commercial 0.05%3.9441 3.9718 0.0277 3.9462 0.0021 7.58 92.4 PRoduct A (with NPE) 5Commercial 0.05% 3.9811 4.0104 0.0293 3.9838 0.0027 9.22 90.8 PRoduct A(with NPE) 6 Commercial 0.05% 3.9515 3.9793 0.0278 3.9546 0.0031 11.1588.8 90.7 PRoduct A (with NPE) 7 Avanel S 150 0.10% 3.9129 3.9390 0.02613.9295 0.0166 63.60 36.4 CGN (as is) 8 Avanel S 150 0.10% 3.8718 3.90090.0291 3.8901 0.0183 62.89 37.1 CGN (as is) 9 Avanel S 150 0.10% 3.85533.8843 0.0290 3.8740 0.0187 64.48 35.5 36.3 CGN (as is) 10 Ultrasil 070.23% 3.7815 3.8088 0.0273 3.7930 0.0115 42.12 57.9 11 Ultrasil 07 0.23%3.9582 3.9865 0.0283 3.9701 0.0119 42.05 58.0 12 Ultrasil 07 0.23%3.8012 3.8288 0.0276 3.8154 0.0142 51.45 48.6 54.8 13 Ultrasil 07 0.23%3.7583 3.7883 0.0300 3.7688 0.0105 35.00 65.0 (130 F.) 14 Ultrasil 070.23% 3.8024 3.8315 0.0291 3.8167 0.0143 49.14 50.9 (130 F.) 15 Ultrasil07 0.23% 3.9351 3.9625 0.0274 3.9497 0.0146 53.28 46.7 54.2 (130 F.) 16Ultrasil 07 0.23% 3.8091 3.8385 0.0294 3.8175 0.0084 28.57 71.4 (2Xcleaning) 17 Ultrasil 07 0.23% 3.9522 3.9801 0.0279 3.9563 0.0041 14.7085.3 (2X cleaning) 18 Ultrasil 07 0.23% 3.9541 3.9816 0.0275 3.95960.0055 20.00 80.0 78.9 (2X cleaning) 19 Lutensol .05%/.05% 3.8701 3.90020.0301 3.8901 0.0200 66.45 33.6 TDA-9/TDA-3 20 Lutensol .05%/.05% 3.98904.0101 0.0211 4.0031 0.0141 66.82 33.2 TDA-9/TDA-3 21 Lutensol .05%/.05%3.9584 3.9874 0.0290 3.9802 0.0218 75.17 24.8 30.5 TDA-9/TDA-3 22 Ethylhexyl 120 ppm/100 ppm 3.7951 3.8244 0.0293 3.8093 0.0142 48.46 51.5sulfate/C12amine oxide 23 Ethyl hexyl 120 ppm/100 ppm 3.7150 3.74240.0274 3.7307 0.0157 57.30 42.7 sulfate/C12amine oxide 24 Ethyl hexyl120 ppm/100 ppm 3.7803 3.8101 0.0298 3.7928 0.0125 41.95 58.1 50.8sulfate/C12amine oxide post cleaning coupon/ coupon/soil Clean soil wtweight % coupon Solution coupon wt soil wt after drying soil % soil %soil removed # Product % Conc. wt. next day next day overnight remainsremains removed average 25 Ecosurf EH-9 0.10% 3.9776 4.0045 0.02693.9803 0.0027 10.04 90.0 26 Ecosurf EH-9 0.10% 3.9512 3.9789 0.02773.9538 0.0026 9.39 90.6 27 Ecosurf EH-9 0.10% 3.7896 3.8167 0.02713.7947 0.0051 18.82 81.2 87.3 28 Ecosurf SA-9 0.10% 3.7420 3.7699 0.02793.7499 0.0079 28.32 71.7 29 Ecosurf SA-9 0.10% 3.9414 3.9691 0.02773.9502 0.0088 31.77 68.2 30 Ecosurf SA-9 0.10% 3.8733 3.9007 0.02743.8852 0.0119 43.43 56.6 65.5 31 Ecosurf EH-3 0.10% 3.7567 3.7852 0.02853.7737 0.017 59.65 40.4 32 Ecosurf EH-3 0.10% 3.8898 3.9177 0.02793.9055 0.0157 56.27 43.7 33 Ecosurf EH-3 0.10% 3.8522 3.8804 0.02823.8673 0.0151 53.55 46.5 43.5 34 Ecosurf .05%/.05% 3.8681 3.8958 0.02773.8849 0.0168 60.65 39.4 EH-3/EH-9 35 Ecosurf .05%/.05% 3.8969 3.92590.0290 3.9101 0.0132 45.52 54.5 EH-3/EH-9 36 Ecosurf .05%/.05% 3.91083.9388 0.0280 3.9279 0.0171 61.07 38.9 44.3 EH-3/EH-9 37 Quadexx 4000.10% 3.7685 3.7992 0.0307 3.7885 0.02 65.15 34.9 38 Quadexx 400 0.10%3.9152 3.9442 0.0290 3.9356 0.0204 70.34 29.7 39 Quadexx 400 0.10%3.8149 3.8448 0.0299 3.8385 0.0236 78.93 21.1 28.5 AVANEL S-150 CGC12-C15 alkyl 15 moles of EO Quadexx 400 is a c6 to c10 EO PO alcoholsurfactantButter-Fat Removal Test 6

TABLE J post total cleaning 10 min PPM coupon/ coupon/soil exposureactives Clean soil soil wt wt (g) weight % time Pdt. in test coupon wt(g) (g) after drying soil (g) % soil % soil removed coupon Productactivity solution wt. (g) next day next day overnight remains remainsremoved average 1 Genapol 100% 1000 ppm 3.5055 3.5328 0.0273 3.52690.0214 78.39 21.6 B2 2 Genapol 100% 1000 ppm 3.5603 3.5897 0.0294 3.58000.0197 67.01 33.0 B2 3 Genapol 100% 1000 ppm 3.5144 3.5403 0.0259 3.53480.0204 78.76 21.2 25.3 B2 4 Genapol 100% 1000 ppm 3.6722 3.7002 0.02803.6978 0.0256 91.43 8.6 EP 2454 5 Genapol 100% 1000 ppm 3.6370 3.66470.0277 3.6590 0.022 79.42 20.6 EP 2454 6 Genapol 100% 1000 ppm 3.52733.5547 0.0274 3.5524 0.0251 91.61 8.4 12.5 EP 2454 7 Berol 840 100% 1000ppm 3.6627 3.6915 0.0288 3.6878 0.0251 87.15 12.8 8 Berol 840 100% 1000ppm 3.5293 3.5585 0.0292 3.5562 0.0269 92.12 7.9 9 Berol 840 100% 1000ppm 3.5769 3.6055 0.0286 3.6043 0.0274 95.80 4.2 8.3 10 Bioterge  38%1000 ppm 3.6692 3.6967 0.0275 3.6858 0.0166 60.36 39.6 PAS-8S 11Bioterge  38% 1000 ppm 3.6307 3.6586 0.0279 3.6497 0.019 68.10 31.9PAS-8S 12 Bioterge  38% 1000 ppm 3.5754 3.6040 0.0286 3.5892 0.013848.25 51.7 41.1 PAS-8S 13 Ecosurf 100% 1000 ppm 3.6388 3.6671 0.02833.6395 0.0007 2.47 97.5 EH-9 14 Ecosurf 100% 1000 ppm 3.5044 3.53230.0279 3.5068 0.0024 8.60 91.4 EH-9 15 Ecosurf 100% 1000 ppm 3.60483.6343 0.0295 3.6079 0.0031 10.51 89.5 92.8 EH-9 16 Ultrasil - 100% 500ppm 3.6033 3.6341 0.0308 3.6036 0.0003 0.97 99.0 01 17 Ultrasil - 100%500 ppm 3.7453 3.7734 0.0281 3.7466 0.0013 4.63 95.4 01 18 Ultrasil -100% 500 ppm 3.4879 3.5165 0.0286 3.4890 0.0011 3.85 96.2 96.9 01 19 DIwater n/a n/a 3.6092 3.6358 0.0266 3.6242 0.0150 56.39 43.6 pH 11.00 20DI water n/a n/a 3.6628 3.6932 0.0304 3.6766 0.0138 45.39 54.6 pH 11.0021 DI water n/a n/a 3.5983 3.6249 0.0266 3.6153 0.017 63.91 36.1 44.8 pH11.00 22 Dehypon 100%, 400, 400, 200 ppm 3.5468 3.5731 0.0263 3.56610.0193 73.38 26.6 LS-54, 100%, 100% Lutensol TO8, Lutensol TO3 23Dehypon 100%, 400, 400, 200 ppm 3.5667 3.5934 0.0267 3.5892 0.0225 84.2715.7 LS-54, 100%, 100% Lutensol TO8, Lutensol TO3 24 Dehypon 100%, 400,400, 200 ppm 3.5260 3.5532 0.0272 3.5488 0.0228 83.82 16.2 19.5 LS-54,100%, 100% Lutensol TO8, Lutensol TO3 25 Ultrasil - 0.19%  1500 ppm3.5827 3.6093 0.0266 3.5972 0.0145 54.51 45.5 02 26 Ultrasil - 0.19% 1500 ppm 3.6156 3.6458 0.0302 3.6332 0.0176 58.28 41.7 02 27 Ultrasil -0.19%  1500 ppm 3.7658 3.7946 0.0288 3.7825 0.0167 57.99 42.0 43.1 02 28Ethyl 40% 30% 300 ppm/100 ppm 3.5026 3.5322 0.0296 3.5196 0.017 57.4342.6 Hexyl Sulfate/ Amine Oxide 29 Ethyl 40%, 30% 300 ppm/100 ppm 3.69353.7217 0.0282 3.7076 0.0141 50.00 50.0 Hexyl Sulfate/ Amine Oxide 30Ethyl 40%, 30% 300 ppm/100 ppm 3.5897 3.6177 0.0280 3.6071 0.0174 62.1437.9 43.5 Hexyl Sulfate/ Amine Oxide Bioterg PaS 8S- Sodium caprylylsulfonateButter-Fat Removal Test 7

For this test Polyvinylidene Difluoride coupons (kynar) were used.

TABLE K post total cleaning 10 min PPM coupon/ coupon/soil exposure timeactives Clean soil soil wt wt (g) weight % Pdt. in test coupon wt (g)(g) after drying soil % soil % soil removed Product activity solution wt(g). next day next day overnight remains remains removed average DIwater n/a n/a 5.5527 5.5791 0.0264 5.5687 0.0160 60.61 39.4 pH 11.00 DIwater n/a n/a 5.4828 5.5091 0.0263 5.4986 0.0158 60.08 39.9 pH 11.00 DIwater n/a n/a 5.5461 5.5740 0.0279 5.5598 0.0137 49.10 50.9 43.4 pH11.00 Ultrasil - 100% 500 ppm 5.5568 5.5853 0.0285 5.5568 0.0000 0.00100.0 01 Ultrasil - 100% 500 ppm 5.4913 5.5189 0.0276 5.4914 0.0001 0.3699.6 01 Ultrasil - 100% 500 ppm 5.4933 5.5209 0.0276 5.4935 0.0002 0.7299.3 99.6 01 Ecosurf 100% 1000 ppm 5.5471 5.5760 0.0289 5.5477 0.00062.08 97.9 EH-9 Ecosurf 100% 1000 ppm 5.6096 5.6382 0.0286 5.6108 0.00124.20 95.8 EH-9 Ecosurf 100% 1000 ppm 5.4500 5.4790 0.0290 5.4506 0.00062.07 97.9 97.2 EH-9 Ultrasil - 65.5%  1506 ppm 5.6890 5.7178 0.02885.6930 0.0040 13.89 86.1 07 Ultrasil - 65.5%  1506 ppm 5.4946 5.52330.0287 5.4973 0.0027 9.41 90.6 07 Ultrasil - 65.5%  1506 ppm 5.56135.5902 0.0289 5.5658 0.0045 15.57 84.4 87.0 07Butter Fat Removal Test 8. (Same Protocol as Test 6).

TABLE L post total cleaning 10 min PPM coupon/ coupon/soil exposure timeactives Clean soil soil wt wt (g) weight % Pdt. in test coupon wt (g)(g) after drying soil % soil % soil removed coupon Product activitysolution wt (g). next day next day overnight remains remains removedaverage 1 DI water n/a n/a 3.6729 3.7009 0.0280 3.6893 0.0164 58.57 41.4pH 11.00 2 DI water n/a n/a 3.7555 3.7818 0.0263 3.7727 0.0172 65.4034.6 pH 11.00 3 DI water n/a n/a 3.6215 3.6487 0.0272 3.6404 0.018969.49 30.5 35.5 pH 11.00 4 Ecosurf 100% 500 ppm 3.4869 3.5136 0.02673.4980 0.0111 41.57 58.4 EH-9 5 Ecosurf 100% 500 ppm 3.9396 3.96730.0277 3.9486 0.009 32.49 67.5 EH-9 6 Ecosurf 100% 500 ppm 3.5867 3.61710.0304 3.5965 0.0098 32.24 67.8 64.6 EH-9 7 Ecosurf 100% 667 ppm 3.63513.6629 0.0278 3.6393 0.0042 15.11 84.9 EH-9 8 Ecosurf 100% 667 ppm3.7337 3.7598 0.0261 3.7366 0.0029 11.11 88.9 EH-9 9 Ecosurf 100% 667ppm 3.8869 3.9163 0.0294 3.8932 0.0063 21.43 78.6 84.1 EH-9 10 Ecosurf100% 832 ppm 3.6224 3.6527 0.0303 3.6265 0.0041 13.53 86.5 EH-9 11Ecosurf 100% 832 ppm 3.6437 3.6677 0.0240 3.6461 0.0024 10.00 90.0 EH-912 Ecosurf 100% 832 ppm 3.7483 3.7733 0.0250 3.7511 0.0028 11.20 88.888.4 EH-9 13 Ecosurf 100% 1000 ppm 3.6459 3.6742 0.0283 3.6498 0.003913.78 86.2 EH-9 14 Ecosurf 100% 1000 ppm 3.5915 3.6167 0.0252 3.5940.0025 9.92 90.1 EH-9 15 Ecosurf 100% 1000 ppm 3.5948 3.6214 0.02663.5976 0.0028 10.53 89.5 88.6 EH-9 16 Ultrasil - 100% 500 ppm 3.62233.6534 0.0311 3.6240 0.0017 5.47 94.5 01 17 Ultrasil - 100% 500 ppm3.4770 3.5055 0.0285 3.4798 0.0028 9.82 90.2 01 18 Ultrasil - 100% 500ppm 3.5413 3.5719 0.0306 3.5434 0.0021 6.86 93.1 92.6 01 19 Ultrasil -65.50%  1506 ppm 3.7020 3.7293 0.0273 3.7120 0.0100 36.63 63.4 07 20Ultrasil - 65.50%  1506 ppm 3.7090 3.7367 0.0277 3.7181 0.0091 32.8567.1 07 21 Ultrasil - 65.50%  1506 ppm 3.5260 3.5443 0.0183 3.53550.0095 51.91 48.1 59.5 07 22 Plurafac 100% 1000 ppm 3.5033 3.5322 0.02893.5255 0.0222 76.82 23.2 SLF-180 23 Plurafac 100% 1000 ppm 3.5309 3.55760.0267 3.5553 0.0244 91.39 8.6 SLF-180 24 Plurafac 100% 1000 ppm 3.63233.6597 0.0274 3.6518 0.0195 71.17 28.8 20.2 SLF-180Butter-Fat Removal Test 9.

TABLE M post total cleaning 10 min PPM coupon/ coupon/soil exposure timeactives Clean soil soil wt wt (g) weight % Pdt. in test coupon wt (g)(g) after drying soil % soil % soil removed coupon Product activitysolution wt (g). next day next day overnight remains remains removedaverage 1 DI water n/a n/a 3.7838 3.8111 0.0273 3.7954 0.0116 42.49 57.5pH 11.00 2 DI water n/a n/a 3.7624 3.7883 0.0259 3.7791 0.0167 64.4835.5 pH 11.00 3 DI water n/a n/a 3.7195 3.7468 0.0273 3.7339 0.014452.75 47.3 46.8 pH 11.00 4 Ultrasil - 100% 500 ppm 3.9048 3.9322 0.02743.9069 0.0021 7.66 92.3 01 5 Ultrasil - 100% 500 ppm 3.7983 3.82520.0269 3.8006 0.0023 8.55 91.4 01 6 Ultrasil - 100% 500 ppm 3.95363.9803 0.0267 3.9561 0.0025 9.36 90.6 91.5 01 7 Ecosurf 100% 1000 ppm3.6755 3.7037 0.0282 3.6817 0.0062 21.99 78.0 EH-9 8 Ecosurf 100% 1000ppm 3.7724 3.8010 0.0286 3.7760 0.0036 12.59 87.4 EH-9 9 Ecosurf 100%1000 ppm 3.7089 3.7348 0.0259 3.7120 0.0031 11.97 88.0 84.5 EH-9 10Ecosurf 100% 1000 ppm 3.9251 3.9516 0.0265 3.9409 0.0158 59.62 40.4 EH-611 Ecosurf 100% 1000 ppm 3.9735 3.9999 0.0264 3.9888 0.0153 57.95 42.0EH-6 12 Ecosurf 100% 1000 ppm 3.9327 3.9592 0.0265 3.9393 0.0066 24.9175.1 52.5 EH-6 13 Ecosurf  90% 1000 ppm 3.6707 3.6982 0.0275 3.67530.0046 16.73 83.3 EH-14 14 Ecosurf  90% 1000 ppm 3.7690 3.7944 0.02543.7740 0.005 19.69 80.3 EH-14 15 Ecosurf  90% 1000 ppm 3.7969 3.82360.0267 3.8052 0.0083 31.09 68.9 77.5 EH-14 16 Afco 4413 as is 10000 ppm3.6526 3.6811 0.0285 3.6741 0.0215 75.44 24.6 17 Afco 4413 as is 10000ppm 3.7367 3.7630 0.0263 3.7552 0.0185 70.34 29.7 18 Afco 4413 as is10000 ppm 3.7862 3.8142 0.0280 3.8054 0.0192 68.57 31.4 28.5 19Ultrasil - as is *26800 ppm 3.7279 3.7580 0.0301 3.7470 0.0191 63.4636.5 110 20 Ultrasil - as is *26800 ppm 4.0383 4.0686 0.0303 4.05520.0169 55.78 44.2 110 21 Ultrasil - as is *26800 ppm 3.7950 3.82500.0300 3.8163 0.0213 71.00 29.0 36.6 110 22 Primus VR as is *7200 ppm3.8123 3.8420 0.0297 3.8354 0.0231 77.78 22.2 2410-486 23 Primus VR asis *7200 ppm 4.0172 4.0476 0.0304 4.0427 0.0255 83.88 16.1 2410-486 24Primus VR as is *7200 ppm 3.8077 3.8376 0.0299 3.8314 0.0237 79.26 20.719.7 2410-486 *pH at 11.5 Afco 4413 is a commercially available membranealkaline cleaning compositionButter-Fat Removal Test 10

TABLE N post 10 min total cleaning exposure PPM coupon/ coupon/soil timeactives Clean soil soil wt wt (g) weight % Product/ test Pdt. in testcoupon wt (g) (g) after drying soil % soil % soil removed pH temp.activity solution wt (g). next day next day overnight remains remainsremoved average DI water 113 F. n/a n/a 3.8824 3.9089 0.0265 3.89770.0153 57.74 42.3 pH 11.00 DI water 113 F. n/a n/a 3.9112 3.9388 0.02763.9253 0.0141 51.09 48.9 pH 11.00 DI water 113 F. n/a n/a 3.8923 3.91900.0267 3.9068 0.0145 54.31 45.7 45.6 pH 11.00 Ultrasil - 01 113 F. 100% 600 ppm 3.8099 3.8394 0.0295 3.8127 0.0028 9.49 90.5 pH 11.00 Ultrasil -01 113 F. 100%  600 ppm 3.7930 3.8213 0.0283 3.7959 0.0029 10.25 89.8 pH11.00 Ultrasil - 01 113 F. 100%  600 ppm 3.7342 3.7631 0.0289 3.73720.003 10.38 89.6 90.0 pH 11.00 LAS acid 113 F. 96% 600 ppm 3.7873 3.81660.0293 3.8072 0.0199 67.92 32.1 pH 11.00 LAS acid 113 F. 96% 600 ppm3.6827 3.7111 0.0284 3.7017 0.019 66.90 33.1 pH 11.00 LAS acid 113 F.96% 600 ppm 3.6439 3.6727 0.0288 3.6601 0.0162 56.25 43.7 36.3 pH 11.00Barlox 12 113 F. 30% 600 ppm 3.9112 3.9395 0.0283 3.9193 0.0081 28.6271.4 pH 11.00 Barlox 12 113 F. 30% 600 ppm 3.9539 3.9828 0.0289 3.96440.0105 36.33 63.7 pH 11.00 Barlox 12 113 F. 30% 600 ppm 3.7856 3.81320.0276 3.7932 0.0076 27.54 72.5 69.2 pH 11.00 VR 2410-486/ 113 F. as is0.03% 3.8912 3.9197 0.0285 3.9038 0.0126 44.21 55.8 blend with vol/volVR 2700-99 6.25 min as is 0.15% 3.7904 3.8194 0.0290 3.8004 0.01 34.4865.5 pH = 10.35 vol/vol VR 2410-486 3.75 min as is 0.70% 3.9124 3.94040.0280 3.9265 0.0141 50.36 49.6 57.0 pH = 11.53 vol/vol Ultrasil - 110113 F. as is 0.40% 3.9369 3.9649 0.0280 3.9532 0.0163 58.21 41.8 pH11.20 vol/vol Ultrasil - 110 113 F. as is 0.40% 3.7027 3.7298 0.02713.7189 0.0162 59.78 40.2 pH 11.20 vol/vol Ultrasil - 110 113 F. as is0.40% 3.7415 3.7695 0.0280 3.7585 0.017 60.71 39.3 40.4 pH 11.20 vol/volVR 2410-486 113 F. as is 0.70% 3.8523 3.8810 0.0287 3.8699 0.0176 61.3238.7 pH 11.70 vol/vol VR 2410-486 113 F. as is 0.70% 3.6953 3.72470.0294 3.7154 0.0201 68.37 31.6 pH 11.70 vol/vol VR 2410-486 113 F. asis 0.70% 3.7027 3.7319 0.0292 3.7223 0.0196 67.12 32.9 34.4 pH 11.70vol/vol EH-9 120 F. as is 1000 ppm 4.0266 4.0556 0.0290 4.0298 0.003211.03 89.0 (10% blend) pH 10.99 EH-9 120 F. as is 1000 ppm 3.7628 3.79140.0286 3.7663 0.0035 12.24 87.8 (10% blend) pH 10.99 EH-9 120 F. as is1000 ppm 3.9396 3.9687 0.0291 3.9435 0.0039 13.40 86.6 87.8 (10% blend)pH 10.99 Ultrasil - 02/ 120 F. as is 0.05% 3.9527 3.9812 0.0285 3.96640.0137 48.07 51.9 blended with vol/vol Na-LAS 120 F. 90% 500 ppm 3.63453.6619 0.0274 3.6530 0.0185 67.52 32.5 90% flake pH 11.00 120 F. 3.72843.7559 0.0275 3.7448 0.0164 59.64 40.4 41.6 Ultrasil - 02/ 120 F. as is0.05% 3.6293 3.6575 0.0282 3.6406 0.0113 40.07 59.9 blended with vol/volUltrasil - 07 120 F. as is 0.05% 3.8889 3.9170 0.0281 3.9069 0.018 64.0635.9 pH 11.00 vol/vol 120 F. 3.8502 3.8777 0.0275 3.8697 0.0195 70.9129.1 41.7 Ultrasil - 02 120 F. as is 0.05% 3.7280 3.7544 0.0264 3.74320.0152 57.58 42.4 pH 11.00 vol/vol Ultrasil - 02 120 F. as is 0.05%3.8515 3.8794 0.0279 3.8641 0.0126 45.16 54.8 pH 11.00 vol/volUltrasil - 02 120 F. as is 0.05% 3.7379 3.7654 0.0275 3.7526 0.014753.45 46.5 47.9 pH 11.00 vol/volButter-Fat Removal Test 11

TABLE O post total cleaning 10 min PPM coupon/ coupon/soil exposure timeactives Clean soil soil wt wt (g) weight % Pdt. in test coupon wt (g)(g) after drying soil % soil % soil removed coupon Product activitysolution wt (g). next day next day overnight remains remains removedaverage 1 DI water n/a n/a 3.9845 4.0118 0.0273 4.0050 0.0205 75.09 24.9pH 11.00 2 DI water n/a n/a 3.9817 4.0099 0.0282 4.0013 0.0196 69.5030.5 pH 11.00 3 DI water n/a n/a 3.9920 4.0194 0.0274 4.0105 0.018567.52 32.5 29.3 pH 11.00 4 Ultrasil - 100% 250 ppm 4.0176 4.0464 0.02884.0220 0.0044 15.28 84.7 01 5 Ultrasil - 100% 250 ppm 3.9806 4.00850.0279 3.9853 0.0047 16.85 83.2 01 6 Ultrasil - 100% 250 ppm 3.93133.9582 0.0269 3.9338 0.0025 9.29 90.7 86.2 01 7 Ultrasil - 100% 500 ppm3.9877 4.0170 0.0293 3.9903 0.0026 8.87 91.1 01 8 Ultrasil - 100% 500ppm 4.0063 4.0351 0.0288 4.0096 0.0033 11.46 88.5 01 9 Ultrasil - 100%500 ppm 3.9860 4.0134 0.0274 3.9881 0.0021 7.66 92.3 90.7 01 25 Ecosurf100% 750 ppm 3.9578 3.9853 0.0275 3.9651 0.0073 26.55 73.5 EH-9 26Ecosurf 100% 750 ppm 4.0320 4.0619 0.0299 4.0379 0.0059 19.73 80.3 EH-927 Ecosurf 100% 750 ppm 4.0057 4.0332 0.0275 4.0129 0.0072 26.18 73.875.8 EH-9 10 Ecosurf 100% 1000 ppm 3.9560 3.9838 0.0278 3.9618 0.005820.86 79.1 EH-9 11 Ecosurf 100% 1000 ppm 4.0028 4.0314 0.0286 4.00750.0047 16.43 83.6 EH-9 12 Ecosurf 100% 1000 ppm 3.9830 4.0107 0.02773.9879 0.0049 17.69 82.3 81.7 EH-9 13 Ecosurf 100% 1250 ppm 3.98014.0098 0.0297 3.9831 0.003 10.10 89.9 EH-9 14 Ecosurf 100% 1250 ppm3.9450 3.9723 0.0273 3.9497 0.0047 17.22 82.8 EH-9 15 Ecosurf 100% 1250ppm 4.0200 4.0487 0.0287 4.0228 0.0028 9.76 90.2 87.6 EH-9 16 Ecosurf100% 1500 ppm 3.9736 4.0015 0.0279 3.9769 0.0033 11.83 88.2 EH-9 17Ecosurf 100% 1500 ppm 3.9607 3.9872 0.0265 3.9677 0.007 26.42 73.6 EH-918 Ecosurf 100% 1500 ppm 3.9558 3.9854 0.0296 3.9617 0.0059 19.93 80.180.6 EH-9 19 Ecosurf 100% 1750 ppm 4.0199 4.0488 0.0289 4.0216 0.00175.88 94.1 EH-9 20 Ecosurf 100% 1750 ppm 4.0509 4.0789 0.0280 4.05480.0039 13.93 86.1 EH-9 21 Ecosurf 100% 1750 ppm 3.9917 4.0208 0.02913.9966 0.0049 16.84 83.2 87.8 EH-9 22 Ecosurf 100% 2000 ppm 3.99854.0267 0.0282 4.0015 0.003 10.64 89.4 EH-9 23 Ecosurf 100% 2000 ppm3.9790 4.0080 0.0290 3.9845 0.0055 18.97 81.0 EH-9 24 Ecosurf 100% 2000ppm 4.0061 4.0337 0.0276 4.0103 0.0042 15.22 84.8 85.1 EH-9Butter-Fat Removal Test 12

TABLE P post total cleaning 10 min PPM coupon/ coupon/soil exposureactives Clean soil soil wt wt (g) weight % time Pdt. in test coupon wt(g) (g) after drying soil % soil % soil removed coupon Product activitysolution wt (g). next day next day overnight remains remains removedaverage 1 EH-Blend 1 95.00% 1000 ppm 3.8989 3.9253 0.0264 3.9096 0.010740.53 59.5 2 EH-Blend 1 95.00% 1000 ppm 3.9832 4.0107 0.0275 3.99480.0116 42.18 57.8 3 EH-Blend 1 95.00% 1000 ppm 3.9905 4.0188 0.02833.9985 0.008 28.27 71.7 63.0 4 EH-Blend 2 97.67% 1000 ppm 3.9748 4.00380.0290 3.9832 0.0084 28.97 71.0 5 EH-Blend 2 97.67% 1000 ppm 4.11644.1470 0.0306 4.1245 0.0081 26.47 73.5 6 EH-Blend 2 97.67% 1000 ppm3.8932 3.9232 0.0300 3.9045 0.0113 37.67 62.3 69.0 7 EH-Blend 3 92.70%1000 ppm 3.9832 4.0123 0.0291 3.9916 0.0084 28.87 71.1 8 EH-Blend 392.70% 1000 ppm 3.9975 4.0267 0.0292 4.0074 0.0099 33.90 66.1 9 EH-Blend3 92.70% 1000 ppm 3.9981 4.0264 0.0283 4.0073 0.0092 32.51 67.5 68.2 10EH-Blend 4 94.27% 1000 ppm 3.9625 3.9909 0.0284 3.9711 0.0086 30.28 69.711 EH-Blend 4 94.27% 1000 ppm 3.9748 4.0058 0.0310 3.9849 0.0101 32.5867.4 12 EH-Blend 4 94.27% 1000 ppm 3.9641 3.9944 0.0303 3.9765 0.012440.92 59.1 65.4 13 EH-Blend 5 93.50% 1000 ppm 3.9581 3.9866 0.02853.9694 0.0113 39.65 60.4 14 EH-Blend 5 93.50% 1000 ppm 3.9846 4.01440.0298 3.9931 0.0085 28.52 71.5 15 EH-Blend 5 93.50% 1000 ppm 3.98484.0136 0.0288 3.9954 0.0106 36.81 63.2 65.0 16 EH-Blend 6 100.0% 1000ppm 3.9276 3.9568 0.0292 3.9357 0.0081 27.74 72.3 (100% EH-9) 17EH-Blend 6 100.0% 1000 ppm 3.9963 4.0255 0.0292 4.0042 0.0079 27.05 72.9(100% EH-9) 18 EH-Blend 6 100.0% 1000 ppm 3.9906 4.0202 0.0296 3.99720.0066 22.30 77.7 74.3 (100% EH-9) 19 DI water n/a n/a 3.9830 4.01300.0300 4.0031 0.0201 67.00 33.0 pH 11.00 20 DI water n/a n/a 3.95873.9882 0.0295 3.9782 0.0195 66.10 33.9 pH 11.00 21 DI water n/a n/a3.9437 3.9725 0.0288 3.9620 0.0183 63.54 36.5 34.5 pH 11.00 22 EH-Blend8 96.50% 1000 ppm 3.9739 4.0026 0.0287 3.9832 0.0093 32.40 67.6 23EH-Blend 8 96.50% 1000 ppm 4.0239 4.0516 0.0277 4.0330 0.0091 32.85 67.124 EH-Blend 8 96.50% 1000 ppm 3.9186 3.9473 0.0287 3.9252 0.0066 23.0077.0 70.6 25 NPE-9.5  100% 500 ppm 4.0648 4.0968 0.0320 4.0706 0.005818.12 81.9 26 NPE-9.5  100% 500 ppm 3.9527 3.9813 0.0286 3.9588 0.006121.33 78.7 27 NPE-9.5  100% 500 ppm 4.0187 4.0468 0.0281 4.0248 0.006121.71 78.3 79.6 Surfactants Activity HLB Ecosurf 100 7.9 EH-3 Ecosurf100 10.8 EH-6 Ecosurf 100 12.5 EH-9 Ecosurf 90 14.2 EH-14 HLB blend % wt(g). EH Blends DI H2O EH-3 EH-6 EH-9 EH-14 activity Blend (in test soln)1 0 0.00 50.00 0.00 50.00 95.00 12.50 0.1052 2 0 0.00 33.33 33.34 33.3397.67 12.50 0.1023 3 0 27.00 0.00 0.00 73.00 92.70 12.50 0.1078 4 021.35 0.00 21.35 57.30 94.27 12.49 0.1060 5 0 17.50 17.50 0.00 65.0093.50 12.50 0.1069 6 0 0.00 0.00 100.00 0.00 100.00  12.50 0.1000 7 1000.00 0.00 0.00 0.00 n/a 0.00 n/a 8 0 0.00 0.00 65.00 35.00 96.50 13.100.1036Butter-Fat Removal Test 13

TABLE Q post total cleaning 10 min PPM coupon/ coupon/soil exposure timeactives Clean soil soil wt wt (g) weight % Pdt. in test coupon wt (g)(g) after drying soil % soil % soil removed coupon Product activitysolution wt (g). next day next day overnight remains remains removedAverage 1 DI water n/a n/a 3.9589 3.9841 0.0252 3.9734 0.0145 57.54 42.5pH 11.00 2 DI water n/a n/a 3.9473 3.9735 0.0262 3.9611 0.0138 52.6747.3 pH 11.00 3 DI water n/a n/a 4.0284 4.0562 0.0278 4.0421 0.013749.28 50.7 46.8 pH 11.00 4 EH-9 +10 ppm 100% 400 ppm 4.0508 4.07660.0258 4.0585 0.0077 29.84 70.2 surfactin EH-9 5 EH-9 +10 ppm 100% 400ppm 4.0420 4.0693 0.0273 4.0482 0.0062 22.71 77.3 surfactin EH-9 6 EH-9+10 ppm 100% 400 ppm 4.0244 4.0501 0.0257 4.0331 0.0087 33.85 66.1 71.2surfactin EH-9 7 EH-9 +10 ppm 100% 600 ppm 4.0545 4.0808 0.0263 4.05880.0043 16.35 83.7 surfactin EH-9 8 EH-9 +10 ppm 100% 600 ppm 3.97944.0059 0.0265 3.9861 0.0067 25.28 74.7 surfactin EH-9 9 EH-9 +10 ppm100% 600 ppm 4.0137 4.0400 0.0263 4.0189 0.0052 19.77 80.2 79.5surfactin EH-9 10 EH-9 +10 ppm 100% 800 ppm 4.2678 4.2937 0.0259 4.27020.0024 9.27 90.7 surfactin EH-9 11 EH-9 +10 ppm 100% 800 ppm 4.03794.0640 0.0261 4.0415 0.0036 13.79 86.2 surfactin EH-9 12 EH-9 +10 ppm100% 800 ppm 3.9546 3.9799 0.0253 3.9564 0.0018 7.11 92.9 89.9 surfactinEH-9 16 Ecosurf EH-9 100% 400 ppm 3.9474 3.9738 0.0264 3.9552 0.007829.55 70.5 17 Ecosurf EH-9 100% 400 ppm 4.0413 4.0682 0.0269 4.04920.0079 29.37 70.6 18 Ecosurf EH-9 100% 400 ppm 4.0087 4.0359 0.02724.0180 0.0093 34.19 65.8 69.0 19 Ecosurf EH-9 100% 600 ppm 3.8929 3.91940.0265 3.8959 0.0030 11.32 88.7 20 Ecosurf EH-9 100% 600 ppm 3.90983.9366 0.0268 3.9139 0.0041 15.30 84.7 21 Ecosurf EH-9 100% 600 ppm4.0168 4.0429 0.0261 4.0227 0.0059 22.61 77.4 83.6 22 Ecosurf EH-9 100%800 ppm 3.9649 3.9925 0.0276 3.9693 0.0044 15.94 84.1 23 Ecosurf EH-9100% 800 ppm 4.0231 4.0496 0.0265 4.0242 0.0011 4.15 95.8 24 EcosurfEH-9 100% 800 ppm 4.0316 4.0591 0.0275 4.0357 0.0041 14.91 85.1 88.3 13Ecosurf EH-9 100% 1000 ppm 3.9662 3.9919 0.0257 3.9663 1E−04 0.39 99.614 Ecosurf EH-9 100% 1000 ppm 4.0391 4.0666 0.0275 4.0405 0.0014 5.0994.9 15 Ecosurf EH-9 100% 1000 ppm 4.0280 4.0552 0.0272 4.0309 0.002910.66 89.3 94.6 25 NPE-9.5 100% 500 ppm 3.9625 3.9888 0.0263 3.9620−0.0005 −1.90 101.9 26 NPE-9.5 100% 500 ppm 4.0835 4.1116 0.0281 4.0833−0.0002 −0.71 100.7 27 NPE-9.5 100% 500 ppm 3.9390 3.9662 0.0272 3.9384−0.0006 −2.21 102.2 101.6 comments, The test solutions containing 10 ppmsurfactant were prepared by adding 6 grams of a 0.1% surfactin solution(prepared in DI) to 594 grams test solution. (test solution containssurfactant and DI water)Butter-Fat Removal Test 14

TABLE R post total cleaning PPM coupon/ coupon/soil actives Clean soilsoil wt wt (g) weight % Pdt. in test coupon wt (g) (g) after drying soil% soil % soil removed coupon Product activity solution wt (g). next daynext day overnight remains remains removed average 1 DI water n/a n/a4.0169 4.0421 0.0252 4.0340 0.0171 67.86 32.1 pH 11.00 2 DI water n/an/a 3.9788 4.0062 0.0274 3.9958 0.017 62.04 38.0 pH 11.00 3 DI water n/an/a 3.9356 3.9621 0.0265 3.9517 0.0161 60.75 39.2 36.4 pH 11.00 4 DIwater n/a n/a 4.0309 4.0582 0.0273 4.0498 0.0189 69.23 30.8 pH 10.00 5DI water n/a n/a 3.9462 3.9748 0.0286 3.9643 0.0181 63.29 36.7 pH 10.006 DI water n/a n/a 3.9565 3.9843 0.0278 3.9742 0.0177 63.67 36.3 34.6 pH10.00 7 DI water n/a n/a 4.0162 4.0434 0.0272 4.0336 0.0174 63.97 36.0pH 9.00 8 DI water n/a n/a 4.0149 4.0422 0.0273 4.0345 0.0196 71.79 28.2pH 9.00 9 DI water n/a n/a 3.9682 3.9963 0.0281 3.9873 0.0191 67.97 32.032.1 pH 9.00 10 EH-9 100% 1000 ppm 4.0664 4.0945 0.0281 4.0697 0.003311.74 88.3 pH 11.00 11 EH-9 100% 1000 ppm 4.0112 4.0400 0.0288 4.01770.0065 22.57 77.4 pH 11.00 12 EH-9 100% 1000 ppm 4.0300 4.0586 0.02864.0345 0.0045 15.73 84.3 83.3 pH 11.00 13 EH-9 100% 1000 ppm 3.95663.9835 0.0269 3.9616 0.005 18.59 81.4 pH 10.00 14 EH-9 100% 1000 ppm3.9016 3.9299 0.0283 3.9070 0.0054 19.08 80.9 pH 10.00 15 EH-9 100% 1000ppm 3.9880 4.0154 0.0274 3.9924 0.0044 16.06 83.9 82.1 pH 10.00 16 EH-9100% 1000 ppm 3.9064 3.9346 0.0282 3.9124 0.0060 21.28 78.7 pH 9.00 17EH-9 100% 1000 ppm 3.8736 3.9012 0.0276 3.8804 0.0068 24.64 75.4 pH 9.0018 EH-9 100% 1000 ppm 4.0068 4.0351 0.0283 4.0152 0.0084 29.68 70.3 74.8pH 9.00 19 NPE-9.5 100% 500 ppm 4.0196 4.0476 0.0280 4.0230 0.0034 12.1487.9 pH 11.00 20 NPE-9.5 100% 500 ppm 4.2305 4.2577 0.0272 4.2322 0.00176.25 93.8 pH 11.00 21 NPE-9.5 100% 500 ppm 3.9203 3.9483 0.0280 3.92280.0025 8.93 91.1 90.9 pH 11.00 22 *No Gel EH-9  95% 1000 ppm 3.93673.9654 0.0287 3.9412 0.0045 15.68 84.3 pH 11.0 23 *No Gel EH-9  95% 1000ppm 3.8987 3.9274 0.0287 3.9034 0.0047 16.38 83.6 pH 11.0 24 *No GelEH-9  95% 1000 ppm 4.1928 4.2221 0.0293 4.1982 0.0054 18.43 81.6 83.2 pH11.0 *Caleb Power formulaA summary of the butterfat removal tests is shown in FIG. 11.Various modifications and additions can be made to the exemplaryembodiments discussed without departing from the scope of the presentdisclosure. For example, while the embodiments described above refer toparticular features, this also includes embodiments having differentcombinations of features and embodiments that do not include all of thedescribed features. Accordingly, the scope of the disclosure is intendedto embrace all such alternatives, modifications, and variations as fallwithin the scope of the claims, together with all equivalents thereof.

What is claimed is:
 1. A method for cleaning a membrane filter system comprising: washing a membrane with a composition comprising a surfactant comprising one or more branched extended nonionic surfactants with a contact angle of less than 20 degrees, and a cloud point of 50° C. or higher, wherein said branched extended nonionic surfactant comprises a surfactant booster having the following formula: R-[L]_(x)-[O—CH₂-CH₂]_(y) where R is a branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 8 to 20 carbon atoms, L is a propylene oxide (PO) linking group, x is the chain length of the linking group ranging from 2-25, and y is the average degree of ethoxylation ranging from 2 to
 20. 2. The method according to claim 1, wherein the membrane is fouled with a food, water, beverage, or brewery product.
 3. The method according to claim 1, wherein the membrane is fouled with a dairy product.
 4. The method according to claim 1 wherein said surfactant booster has an R group of ethyl hexyl.
 5. The method according to claim 4 wherein said surfactant booster has an R group of 2 ethyl hexyl.
 6. The method according to claim 1 wherein x is
 5. 7. The method according to claim 1 wherein said y is 6 or
 9. 8. The method according to claim 1 wherein said branched extended nonionic surfactant further comprises a Guerbet alcohol.
 9. The method according to claim 8 wherein said Guerbet alcohol is a 3 propyl heptanol C₁₀-(PO)_(a)(EO)_(b) series, where a is 1.0 to 1.5, b is 4 to 14, PO is propylene oxide, and EO is ethylene oxide.
 10. The method according to claim 1 wherein said membrane is a polyethersulfone membrane.
 11. The method according to claim 1 wherein said membrane is a polyvinylidene fluoride membrane.
 12. The method according to claim 1 wherein said membrane is a polyamide and/or thin film composite membrane.
 13. The method according to claim 1 wherein said membrane is a ceramic membrane.
 14. The method according to claim 1 wherein said membrane is a stainless steel membrane.
 15. The method according to claim 1 wherein said composition has an interfacial tension of less than 7 mN/m.
 16. The method according to claim 1, further comprising washing said membrane with a source of alkalinity.
 17. The method according to claim 16 wherein said washing of said membrane with a source of alkalinity occurs prior to, simultaneous with or after said washing of said membrane with said surfactant.
 18. The method according to claim 1 wherein said method does not include the application of nonyl phenol ethoxylates (NPE) to said membrane.
 19. A method of cleaning a filtration membrane comprising: applying to said membrane a cleaning composition comprising; a source of alkalinity; and one or more branched extended nonionic surfactants with a contact angle of less than 20 degrees, a cloud point of 50° C. or higher wherein said branched extended nonionic surfactant comprises a surfactant booster having the following formula: R-[L]_(x)-[O—CH₂-CH₂]_(y) where R is a branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 8 to 20 carbon atoms, L is a propylene oxide (PO) linking group, x is the chain length of the linking group ranging from 2-25, and y is the average degree of ethoxylation ranging from 2 to 20 and thereafter, rinsing said membrane, wherein said cleaning composition is NPE free.
 20. The method according to claim 19 wherein said extended surfactant has an R group of 2 ethyl hexyl.
 21. The method according to claim 19 wherein x is
 5. 22. The method according to claim 19 wherein said y is 6 or
 9. 23. The method according to claim 19 wherein said cleaning composition further comprises a Guerbet alcohol.
 24. The method according to any of claim 23 wherein said Guerbet alcohol is a 3 propyl heptanol C₁₀-(PO)_(a)(EO)_(b) series, where a is 1.0 to 1.5, and b is 4 to
 14. 25. The method according to claim 19 wherein said membrane is a polyethersulfone membrane.
 26. The method according to claim 19 wherein said membrane is a polyvinylidene fluoride membrane.
 27. The method according to claim 19 wherein said membrane is a polyamide and/or thin film composite membrane.
 28. The method according to claim 19 wherein said membrane is a ceramic membrane.
 29. The method according to claim 19 wherein said membrane is a stainless steel membrane.
 30. The method according to claim 19 wherein said composition has an interfacial tension of less than 7 mN/m.
 31. A method of cleaning a filtration membrane comprising: Mixing water with one or more branched extended nonionic surfactants with a contact angle of less than 20 degrees, a cloud point of 50° C. or higher wherein said branched extended nonionic surfactant comprises a surfactant booster having the following formula: R-[L]_(x)-[O—CH₂-CH₂]_(y) where R is a branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 8 to 20 carbon atoms, L is a propylene oxide (PO) linking group, x is the chain length of the linking group ranging from 2-25, and y is the average degree of ethoxylation ranging from 2 to 20 and thereafter, flushing said membrane with water and said surfactant mixture.
 32. The method according to claim 31 wherein said extended surfactant has an R group of 2 ethyl hexyl.
 33. The method according to of claim 31 wherein x is
 5. 34. The method according to claim 31 wherein said y is 6 or
 9. 35. The method according to claim 31 wherein said cleaning composition further comprises a Guerbet alcohol.
 36. The method according to claim 31 wherein said membrane is a polyvinylidene fluoride membrane. 